Method of manufacturing a water- and oil-repelling film having surface irregularities

ABSTRACT

A water- and oil-repelling adsorbing film formed on a material having active hydrogen such as hydroxyl group, imino group and amino group at the surface. This film is a chemically adsorbed film having surface irregularities exceeding 10 nanometers. It is directly or indirectly covalently bonded to the material surface and includes a monomolecular film or a polymer film with the molecules thereof containing a fluorocarbon group and a --Si-- bond. The surface irregularities which exceed the molecular level are at least either those formed on the material surface itself, those due to particles formed on the substrate surface or those due to particles present in the chemically adsorbed film.

This application is a division of Ser. No. 07/824,287, filed Jan. 23,1992, now U.S. Pat. No. 5,324,566.

BACKGROUND OF THE INVENTION

The present invention relates to water- and oil-repelling adsorbed filmswhich can be used on electric products, vehicles and industrialapparatus requiring such a film and a method of manufacturing the same.

The invention further relates to water- and oil-repelling,anti-contaminating glass, ceramic, metal and plastic products and amethod of manufacturing such products.

DESCRIPTION OF THE PRIOR ART

Heat-, weather- and wear-resistant super-thin coating films are desiredfor electric products, vehicles, industrial apparatus, mirrors and glasslenses.

Hitherto, coatings which have been extensively used for water- andoil-repelling purposes, has been produced by the surface roughening ofan Al substrate or the like by means of blasting, a wire brush orchemical etching, and then coating a primer followed by a fluorineenamel coating or like paint. The coatings can be prepared by suspendingfine fluorocarbon base particles of polyethylenetetrafluoride inethanol, followed by drying and baking (or fixing) at about 400° C. forabout one hour to affix the fluorocarbon based polymer to the substratesurface.

However, while this method permits ready manufacture, the polymer isbonded to the substrate by a mere anchor effect, thus imposinglimitations on the adhesion of the polymer to the substrate. Inaddition, since the coating film surface is baked at a high temperatureof 400° C., it is flattened, and it was impossible to obtain asatisfactorily water- and oil-repelling surface. The method, therefore,was insufficient for electric products, vehicles, industrial apparatusand so forth requiring water- and oil-repelling coating films.

The water- and oil-repelling properties have also been required forglass, ceramic, metal and plastic products, typically such glassproducts as vehicle window glass and front glass, optical lenses, glasslenses and building window glass, such ceramic products as sanitaryporcelain, table dishes and flower vases, such construction materials asdoor and window sashes, metal materials for building exterior walls andsuch plastic products as furniture, cover films, decoration boards andpanels.

Further, it has been a sole way of preventing contamination of theglass, ceramic, metal and plastic products to make the surface of theproducts as smooth as possible. It is a known practice to coathydrophilic polymer for preventing the fogging of the glass surface.However, this provides only a tentative effect. It is also a knownpractice to coat a metal surface with a fluorine resin or the like. Thisis done by thinly coating a fluorine enamel and then baking the same. Asanother means of resin coating, a paint is dissolved or suspended in asolvent, and the suspension or solution is coated, followed by drying ofthe solvent and hardening by baking.

With the above method of fluorine resin coating, however, the obtainedsurface has irregularities on the order of several tens of microns, andtherefore it is difficult to obtain a surface having excellent luster.In addition, the coating has inferior adhesion to the substrate, andhigh durability can not be obtained. Further, other resin coatings areinferior in adhesion strength, posing problems in durability. This isdue to the fact that adhesion to the substrate is based on physicaladsorption.

To solve the above problems inherent in the prior art, the presentinvention has an object of providing a coating film, which has strongadhesion to the substrate, is free from pin holes, has desirable surfaceirregularities and is excellently water- and oil-repelling and durable.

Another object of the invention is to provide a method of producing afluorine-based monomolecular film, which has satisfactory adhesion tothe substrate, is free from pin holes, has desirable surfaceirregularities and is excellently water- and oil-repelling for improvingthe performance of products requiring heat-, weather- and wear-resistantwater-and oil-repelling coatings such as buildings, electric products,vehicles and industrial apparatus.

SUMMARY OF THE INVENTION

An objective of the invention is to provide a water- and oil-repellingadsorbing film formed on a substrate surface, the adsorbing film being achemically adsorbed film having surface irregularities exceeding 10nanometers, the chemically adsorbed film being bonded by covalent bondsto the substrate surface either directly or indirectly, and thechemically adsorbed film being a monomolecular or polymer film with themolecules thereof containing a fluorocarbon group and a siloxane group.

It is preferable in this invention that the surface irregularities arefrom irregularities formed on the substrate surface itself,irregularities due to fine particles formed on the substrate surface orirregularities due to fine particles present in the chemically adsorbedfilm.

It is preferable in this invention that the particles formed on thesubstrate surface and fine particles in the chemically adsorbed film arehydrophilic particles.

It is preferable in this invention that the hydrophilic particles andthe polymer with the molecule thereof containing a fluorocarbon groupand a siloxane group are bonded to one another by covalent bonds.

It is preferable in this invention that the surface irregular chemicallyadsorbed film is bonded by covalent bonds of --SiO-- or --SiN═ to thesubstrate surface.

It is preferable in this invention that comprises a thin layer ofpolysiloxane or a thin layer of chemically adsorbed monomolecular layerof siloxane formed on the substrate surface and a surface irregular filmformed on the thin layer or the chemically adsorbed monomolecular layer.

It is preferable in this invention that the substrate surface isprovided with irregularities formed by particles and/or a coated layerincorporating silicate glass and having surface irregularities and athin layer or a chemically adsorbed monomolecular layer with themolecules thereof containing a fluorocarbon group and a siloxane group,the surface irregular layer and the thin layer or chemically adsorbedmonomolecular layer being bonded to each other by siloxane bonds.

It is preferable in this invention that the substrate is made of atleast a member of a group consisting of glass, ceramics, metals,plastics, wood, stone and semiconductors.

It is preferable in this invention that the substrate surface isprovided with irregularities at a level less than the wavelength ofvisible light, and which is a anti-contaminating.

It is preferable in this invention that the substrate is a plastic film.

It is preferable in this invention that the plastic film has a coarsenedsurface with surface irregularities at a level less than 0.3micrometers.

Another objective of this invention is to provide a method ofmanufacturing a water- and oil-repelling adsorbing film comprising:

making a substrate surface irregular; and

contacting the irregular surface with a non-aqueous solution containingan active surface material having a fluorocarbon group and achlorosilane group or having a fluorocarbon group and an alkoxysilanegroup.

It is preferable in this invention wherein comprising at least thefollowing steps A to D:

A. forming the substrate surface having surface active hydrogen groupswith surface irregularities and/or then providing the substrate surfacewith active hydrogen groups;

B. contacting the substrate surface with a silane-based surface activematerial with the molecules thereof containing a silyl group at one endand a fluorocarbon group at the other end to adsorb the surface activematerial to the substrate surface by a dehydrochlorination reaction or adealcoholation reaction;

C. forming an outer layer by reacting with water with or withoutprevious removal of non-reacted surface active material by washing usinga non-aqueous organic solution; and

D. drying or thermally treating the substrate surface.

It is preferable in this invention wherein comprising at least thefollowing steps a to f:

a. forming the substrate surface having .active hydrogen groups withsurface irregularities and/or then providing the substrate surface withactive hydrogen groups;

b. contacting the substrate surface with a non-aqueous solutioncontaining a surface active material with the molecules thereof having aplurality of chlorosilyl groups to adsorb the surface active material bya dehydrochlorination reaction;

c. forming an inner layer by reacting with water with or withoutprevious removal of non-reacted surface active material by washing witha non-aqueous organic solution;

d. contacting the surface of the inner layer with a silane-based surfaceactive material with the molecule thereof containing a silyl group atone end and a fluorocarbon group at the other end to adsorb the surfaceactive material to the substrate surface by a dehydrochlorinationreaction or a dealcoholation reaction;

e. forming an outer layer by reacting with water with or withoutprevious removal of non-reacted surface active material by washing witha non-aqueous organic solution; and

f. drying or thermally treating the substrate surface.

It is preferable in this invention that the substrate surface isprovided or formed with irregularities by:

mixing fine particles and silicate glass on the substrate surface andthen thermally baking the coating together with the substrate,electrolytic etching, chemical etching, sand blasting, spattering,depositing, or rubbing..

It is preferable in this invention that the chlorosilyl-based surfaceactive material is one with the molecules thereof having at one end achlorosilane group represented by a formula;

    --SiCl.sub.n X.sub.3-n

where n represents an integer from 1 to 3, and X represents at least onefunctional group selected from the group consisting of a lower-alkylgroup and a lower-alkoxyl group.

It is preferable in this invention that the silane-based surface activematerial is a compound selected from a group consisting of

    CF.sub.3 --(CF.sub.2).sub.n --T--SiY.sub.p Cl.sub.3-p

where n represents an integer from 1 to 25, T represents a member of thegroup consisting of an alkyl group, an ethylene group, an acetylenegroup and a substituted group containing a silicon atom and a hydrogenatom, Y represents a substituted group selected from the groupconsisting of an alkyl group, a cycloalkyl group, an aryl group andderivatives of these groups, and p represents a number selected from thegroup consisting of 0, 1 and 2, and

    CF.sub.3 --(CF.sub.2).sub.n --T'--SiZ.sub.q (OA).sub.3-q

where n represents either 0 or an integer, T' represents a member of thegroup consisting of an alkyl group, an alkylene group, an alkyne group,and a substituted group containing a silicon atom and a hydrogen atom, Zrepresents a substituted group selected from a group consisting of analkyl group, a cycloalkyl group, an aryl group and derivatives thereof Arepresents a hydrogen atom or an alkyl group, and q represents 0, 1 or2.

It is preferable in this invention that the surface active material withthe molecules thereof containing a plurality of chlorosilyl groups is acompound selected from the group consisting of SiCl₄, SiHCl₃, SiH₂ Cl₂,and Cl--(SiCl₂ O)_(n) --SiCl₃, where n is an integer from 1 to 10.

It is preferable in this invention that the substrate having hydroxylgroups at the surface is a plastic substrate with the surface thereoftreated in an oxygen-containing plasma atmosphere to be hydrophilic.

It is preferable in this invention that the active hydrogen group on thesubstrate surface is a member of the group consisting of a hydroxylgroup, an amino group and an imino group.

It is preferable in this invention that the non-aqueous solutioncontaining a chlorosilyl-based surface active material contains acrosslinking agent selected from the group consisting of SiP_(s)Cl_(4-s) where P represents H, a lower-alkyl group and a lower-alkoxylgroup, and s represents of 0, 1 and 2, and SiQ_(t) (OA)_(4-t) where Q isat least one substituted group selected from the group consisting of alower-alkyl group and a lower-alkoxyl group, A represents hydrogen atomor a lower-alkyl group, and t represents 0, 1 or 2.

Another objective of this invention is to provide a method ofmanufacturing a water- and oil-repelling adsorbing film comprising:

preparing a substrate having active hydrogen groups at the surface andcontacting the substrate with a non-aqueous solution containing amaterial with the molecules thereof having a plurality of chlorosilylgroups to coat the material onto the surface of the substrate through areaction between active hydrogen groups at the substrate surface and thechlorosilyl groups of the material with the molecules thereof having aplurality of chlorosilyl groups;

coating with a non-aqueous solution containing a mixture of the surfaceactive material with the molecules thereof containing a fluorocarbongroup and a chlorosilane group and fine particles having a hydrophilicsurface;

contacting with a mixture of a material with the molecules thereofcontaining a fluorocarbon group and an alkoxysilane group and fineparticles having hydrophilic surface; and

thermally baking the coating together with the substrate.

Another objective of this invention is to provide a method ofmanufacturing a water- and oil-repelling adsorbing film comprising:

a step of preparing a substrate having active hydrogen groups at thesurface and contacting the surface of the substrate with a non-aqueoussolution containing a material with the molecules thereof containing aplurality of chlorosilyl groups to adsorb the material to the substratesurface through a reaction between active hydrogen groups on thesubstrate surface and chlorosilyl groups of the material with themolecules thereof having a plurality of chlorosilyl groups;

forming a thin film or a chemically adsorbed monomolecular film of thematerial with the molecules thereof containing a plurality ofchlorosilyl groups on the substrate with or without removal ofnon-reacted material remaining on the substrate by washing with anon-aqueous organic solution;

adsorbing a non-aqueous solution containing a mixture of a surfaceactive material with the molecules thereof having a fluorocarbon groupand a silyl group and fine particles having hydrophilic surface; and

thermally baking the coating together with the substrate.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic sectional view for explaining a process ofmanufacture as in example 1 of the invention;

FIG. 2 is a sectional view, enlarged to a molecular level, showing thesame;

FIG. 3 is a sectional view, enlarged to a molecular level, showing thesame, i.e., portion A in FIG. 4;

FIG. 4 is a schematic sectional view for explaining the coating film inthe first example of the invention;

FIG. 5 is a schematic sectional view for explaining a process ofmanufacture as in example 2 of the invention;

FIG. 6 is a sectional view, enlarged to a molecular level, showing thesame;

FIG. 7 is a sectional view, enlarged to a molecular level, showing thesame, i.e., portion B in FIG. 8; and

FIG. 8 is a schematic sectional view for explaining the coating film inthe example 2 of the invention;

FIG. 9 is a schematic view, enlarged to a molecular level, showing asubstrate prior to the process as in example 3 of the invention;

FIG. 10 is a schematic view, enlarged to a molecular level, showing theprocess as in example 3 of the invention;

FIG. 11 is a schematic view, enlarged to a molecular level, showing theprocess as in example 3 of the invention;

FIG. 12 is a schematic view, to an enlarged scale, showing the processas in example 3 of the invention;

FIG. 13 is a schematic view, to an enlarged scale, showing a water- andoil-repelling film obtained as in example 3 of the invention;

FIG. 14 is a schematic view, enlarged to a molecular level, showing asubstrate prior to the process as in example 3 of the invention;

FIG. 15 is a schematic view, enlarged to a molecular level, showing theprocess as in example 3 of the invention;

FIG. 16 is a schematic view, enlarged to a molecular level, showing theprocess as in example 3 of the invention;

FIG. 17 is a schematic view, enlarged to a molecular level, showing theprocess as in example 3 of the invention;

FIG. 18 is a schematic view, to an enlarged scale, showing a water- andoil-repelling film obtained as in example 3 of the invention;

FIG. 19 is a schematic view, enlarged to a molecular level, showing asubstrate prior to the process as in example 4 of the invention;

FIG. 20 is a schematic view, enlarged to a molecular level, showing theprocess as in example 4 of the invention;

FIG. 21 is a schematic view, enlarged to a molecular level, showing theprocess as in example 4 of the invention;

FIG. 22 is a schematic view, enlarged to a molecular level, showing astate after the process as in example 4 of the invention;

FIG. 23 is a schematic view, at an enlarged scale, showing a water- andoil-repelling film obtained as in example 4 of the invention;

FIG. 24 is a schematic view, enlarged to a molecular level, showing asubstrate prior to the process aws in example 4 of the invention;

FIG. 25 is a schematic view, enlarged to a molecular level, showing theprocess as in example 4 of the invention;

FIG. 26 is a schematic view, enlarged to a molecular level, showing theprocess as in example 4 of the invention;

FIG. 27 is a schematic view, enlarged to a molecular level, showing astate after the process as in example 4 of the invention;

FIG. 28 is a schematic view, to an enlarged scale, showing a water- andoil-repelling film obtained as in example 4 of the invention:

FIG. 29 is a schematic sectional view for explaining a process ofmanufacturing a water- and oil-repelling process as in example 5 of theinvention;

FIG. 30 is a schematic view for explaining a process of manufacturing awater- and oil-repelling coating film as in example 5 of the invention;

FIG. 31 is a schematic sectional view showing what happens when waterdrops strike a water- and oil-repelling coating film as in example 5 ofthe invention;

FIG. 32 is a schematic sectional view, enlarged to a molecular level,showing the water- and oil-repelling coating film, i.e., a portion C asin FIG. 30;

FIG. 33 is a schematic sectional view, enlarged to a molecular level,showing a water- and oil-repelling coating film in the form of amonomolecular film as in example 9 of the invention:

FIG. 34 is a schematic sectional view for explaining a process ofmanufacture of a water- and oil-repelling process as in example 10 ofthe invention:

FIG. 35 is a schematic sectional view for explaining a process ofmanufacturing a water- and oil-repelling coating film as in example 10of the invention;

FIG. 36 is a schematic sectional view showing what happens when waterdrops strike the water- and oil-repelling coating film according to theinvention:

FIG. 37 is a schematic sectional view, enlarged to a molecular level,showing a water- and oil-repelling coating film, i.e., a portion D as inFIG. 35;

FIG. 38 is a schematic sectional view, enlarged to a molecular level,showing a water- and oil-repelling coating film as in example 10 of theinvention:

FIG. 39 is a sectional view showing a glass substrate having a coarsenedsurface used as in example 13 of the invention;

FIG. 40 is a schematic sectional view, enlarged to a molecular level,having the surface of a glass substrate with a monomolecular film formedthereon as in example 13 of the invention;

FIG. 41 is a schematic view, enlarged to a molecular level, showing thesurface of an aluminum substrate prior to the film forming process as inexample 14 of the invention;

FIG. 42 is a schematic sectional view showing a process of manufacturinga siloxane-bonded monomolecular film as in example 14 of the invention;

FIG. 43 is a schematic sectional view showing a process of manufacturinga fluorine-based monomolecular film as in example 14 of the invention;

FIG. 44 is a schematic sectional view, to an enlarged scale, showing thesurface of a transparent glass plate with a water- and oil-repellingcontamination-proof outer surface and an anti-fogging inside surface asin example 14 of the invention;

FIG. 45(a) is a schematic sectional view showing a polyethylenetetrachloride film prior to formation of a water- and oil-repelling filmas in example 15 of the invention;

FIG. 45(b) is a schematic sectional view, enlarged to a molecular level,showing a portion E of film surface (a) after formation of the water-and oil-repelling film on the polyethylene tetrachloride as in example15 of the invention;

FIG. 46(a) is a schematic sectional, enlarged to a molecular level,showing film surface prior to formation of a water- and oil-repellingfilm on a poly(ethylene terephthalate) film as in example 16 of theinvention;

FIG. 46(b) is a schematic sectional view, enlarged to a molecular level,showing a poly(ethylene terephthalate) film surface during formation ofthe water- and oil-repelling film as in example 16 of the invention;

FIG. 46(c) is a schematic sectional view, enlarged to a molecular level,showing the poly(ethylene terephthalate) film surface after formation ofthe water- and oil-repelling film as in example 16 of the invention;

DETAILED DESCRIPTION OF THE INVENTION

A water- and oil-repelling adsorbing film formed on a material havingactive hydrogen such as hydroxyl group, imino group and amino group atthe surface. This film is a chemically adsorbed film having surfaceirregularities exceeding 10 nanometers. It is directly or indirectlycovalently bonded to the material surface and includes a monomolecularfilm or a polymer film with the molecules thereof containing afluorocarbon group and a --Si-- group. The surface irregularities whichexceed the molecular level are at least either those formed on thematerial surface itself, those due to particles formed on the substratesurface or those due to particles present in the chemically adsorbedfilm.

According to the invention, an irregular thin surface film, which iseither a coating film of a mixture of a polymer of a material having afluorocarbon group and a chlorosilane group and hydrophilic, finesurface particles or a coating film of a mixture of a polymer with themolecules thereof containing a fluorocarbon group and a siloxane(--SiO--) group and hydrophilic, fine surface particles, is formed on asubstrate surface such that it is chemically bonded thereto via a thinfilm of polysiloxane or a chemically adsorbed monomolecular film ofsiloxane. Thus, it is possible to obtain a coating film, whichsatisfactorily adheres to the substrate surface, is substantiallypin-hole free has surface irregularities at the micron level and isexcellent in water- and oil-repelling properties and durability.

In a method according to the invention, using a substrate havinghydroxyl groups at the surface, a non-aqueous solution containing amaterial having a plurality of chlorosilyl groups is coated on thesubstrate to obtain a thin film having numerous --SiOH bonds on thesubstrate surface through a reaction between hydroxyl groups of thesubstrate surface and chlorosilyl groups in the material with themolecules thereof having a plurality of chlorosilyl groups. Bysubsequently coating with a non-aqueous solution containing a mixture ofa material with the molecules thereof a fluorocarbon group and achlorosilane group and hydrophilic, fine surface particles or with asolution containing a mixture of a material having a fluorocarbon groupand an alkoxysilane group and hydrophilic, fine surface particles andthen thermally baking (i.e., heating or curing) the coating togetherwith the substrate in a moisture-containing atmosphere, afluorocarbon-based coating film is chemically bonded by --SiO-- bonds tothe thin film having numerous --SiOH bonds formed in the preceding stepon the substrate surface through a dehydrochlorination or dealcoholationreaction brought about between chlorosilane groups and alkoxysilanegroups or between these groups and --SiOH groups of the thin film havingnumerous --SiO-- bonds. The fluorocarbon-based coating film here isformed such that hydrophilic, fine surface particles are taken in by theafore-mentioned surface.

Meanwhile, in the step of coating with the non-aqueous solutioncontaining the material with the molecule thereof having a plurality ofchlorsilyl groups, subsequent to coating with the non-aqueous solutionwith the molecule thereof having a plurality of chlorosilyl groups forthe reaction between hydroxyl groups of the substrate surface andchlorosilyl groups in the material with the molecules thereof having aplurality of chlorosilyl groups, by washing away excess material havinga plurality of chlorosilyl groups remaining on the substrate by using anon-aqueous organic solution and then carrying out water washing, apolysiloxane-based chemically adsorbed monomolecular film with themolecules thereof having a plurality of silanol (--SiOH) groups can beformed on the substrate.

In this method, all the --SiOH bonds formed on the substrate surface arebonded to the substrate by siloxane bonds. Thus, by adsorbing themonomolecular film having the --SiO-- bonds with a non-aqueous solutioncontaining a mixture of a material with the molecules thereof having afluorocarbon group and a chlorosilane group and hydrophilic surface fineparticles or with a solution containing a mixture of a material having afluorocarbon group and an alkoxysilane group and hydrophilic surfacefine particles and thermally baking the coating together with thesubstrate in a moisture-containing atmosphere, a polymer containing afluorocarbon group is chemically bonded via --SiO-- bonds to thesubstrate through a dehydrochlorination reaction or dealcoholationreaction brought about between chlorosilane groups and alkoxysilanegroups or between these groups and --OH groups of the polysiloxane-basedmonomolecular film having numerous --SiO-- bonds formed in the precedingstep in the substrate surface.

Thus, it is possible to produce a fluorocarbon-based adsorbing film withexcellent adhesion and such that hydrophilic, fine surface particles aretaken in by the aforementioned surface. If the thickness of thefluorocarbon-based adsorbing film is set at this time to be smaller thanthe diameter of the hydrophilic, fine surface particles, theaforementioned surface is naturally made irregular by the hydrophilic,fine surface particles. In addition, like the substrate surface thesurfaces of the hydrophilic, fine surface particles are covered by thefluorocarbon-based adsorbing film. Thus, a florocarbon-based coatingfilm can be formed, which is excellent in water- and oil-repellingproperties and has desired surface irregularities.

The extent or level of the surface irregularities can be controlledaccording to the diameter and amount of the fine particles to be added.As the substrate having hydroxyl groups at the surface a metal orceramic substrate may be used with the surface thereof covered by anatural oxide film. If a plastic or like substrate without any oxidefilm on the surface is to be used, its surface may be renderedhydrophilic in advance through treatment in an oxygen-containing plasmaor corona atmosphere.

As the hydrophilic surface fine particles those of metals, ceramics,glass, stone, etc. may be used with the surface thereof covered by anatural oxide film. If plastic or like fine particles without anysurface oxide film are to be used, their surface may be rendered to behydrophilic in advance through a treatment in an oxygen-containingplasma or corona atmosphere.

Further, according to the invention a fluorine-containing chemicallyadsorbed monomolecular film is formed by siloxane bonds to the surfaceof a substrate after a surface toughening treatment thereof. It is thuspossible to obtain a fluorine-based coating film, which issatisfactorily adhered to the substrate, is substantially pin-hole free,has desirable surface irregularities, has excellent water- andoil-repelling properties, is heat-resistant, weather-resistant,anti-contaminating, wear-resistant, etc.

Further, according to the invention by including a step of preliminarilyforming a glass coating film having surface irregularities on the orderof from sub-microns to microns on the surface of a fluorocarbon-basedcoating film by coating with a mixture of fine glass particles andsilicate glass and baking the coating, or a step of coarsening thesubstrate by etching with a sand blast treatment, it is possible toprovide the surface of a florocarbon-based coating film produced in asubsequent step with fine surface irregularities. Thus, it is possibleto form a fluorocarbon-based coating film, which has desirable surfaceirregularities and excellent water- and oil-repelling properties.

The polymer containing a fluorocarbon group excellent adhesion for it ischemically bonded to the substrate by --SiO-- or --SiN═ covalent bonds.

In the method of coating with fine particles, the extent of surfaceirregularities can be controlled according to the diameter and amount offine particles to be added to the silicate glass.

Further, by inserting subsequent to the step of forming surfaceirregularities a step of contacting the substrate with a non-aqueoussolution containing a material having a plurality of chlorosilyl groupsto cause precipitation of the material with the molecule thereofcontaining a plurality of chlorosilyl groups on the substrate surfacethrough a reaction brought about between hydroxyl groups of thesubstrate surface and chlorosilyl groups of the material and a step ofremoving excess material with the molecule thereof containing aplurality of chlorosilyl groups remaining on the substrate by washingwith a non-aqueous organic solvent and then causing reaction with water,and carrying out a step of causing chemical adsorption to the substratesurface of a chlorosilane-based surface active material having achlorosilane (--SiCl_(n) X_(3-n), n represents from 1 to 3, X representsa functional group) group at one end and a straight chain fluorocarbongroup at the other end, a chemically adsorbed monomolecular fluorocarbonfilm can be produced, which has a higher molecular adsorption density.

As the material with the molecule thereof containing a chlorocarbongroup and a chlorosilane group may be used

    CF.sub.3 --(CF.sub.2).sub.n --T--SiY.sub.p Cl.sub.3-p

and as the material with the molecules thereof having a fluorocarbongroup and an alkoxyl group may be used

    CF.sub.3 --(CF.sub.2).sub.n --T'--SiZ.sub.q (OA).sub.3-q

Further, for adjusting the hardness of the fluorocarbon-based polymerfilm, as the crosslinking agent may be use SiX_(s) Cl_(4-s) where Xrepresents a hydrogen atom or a substituted group such as an alkyl groupand s represents 0, 1, or 2, or

    SiY.sub.t (OA).sub.4-t

where A represents an alkyl group and t represents 0, 1, or 2. By sodoing, the density of three-dimensional bridging in the producedfluorocarbon-based polymer film may be adjusted. That is, the hardnessof the fluorocarbon-based polymer film having desirable surfaceirregularities can be controlled.

Further, the water- and oil-repelling coating film according to theinvention comprises at least a layer of a mixture of fine particles andsilicate glass having desirable surface irregularities and a polymer orchemically adsorbed monomolecular layer containing a fluorocarbon groupand a siloxane group. Thus, it is possible to obtain a coating film,which is satisfactorily adhered to the substrate, is substantiallypin-hole free, has surface irregularities measurable at the micron leveland is excellent, in its water- and oil-repelling properties.

Further, by including in the method of manufacture according to theinvention a step of producing a coating film having surfaceirregularities measurable at the micron level on the surface of asubstrate for forming a fluorocarbon-based coating film or a chemicallyadsorbed monomolecular film by coating the surface with a mixture offine glass particles and silicate glass, it is possible to provide afluorocarbon-based coating film produced in a subsequent step with finesurface irregularities. Thus, it is possible to form afluorocarbon-based polymer or chemically adsorbed monomolecular film,which has desirable surface irregularities and has excellent water-andoil-repelling properties. In this case, the polymer containingfluorocarbon groups are chemically bonded by --O-- bonds to thesubstrate, and thus excellent adhesion can be obtained.

The extent or level of surface irregularities can be controlledaccording to the diameter and amount of fine particles added to silicateglass.

By so doing, the density of three-dimensional crosslinking in thefluorocarbon-based polymer film thus produced can be adjusted. That is,the hardness of the fluorocarbon-based polymer film having desirablesurface irregularities can be controlled.

According to the invention, there is thus provided a method ofmanufacturing a coating film having desirable surface irregularities andexcellent water- and oil-repelling properties comprising a step ofcoating the surface of a coating film substrate with a mixture of fineglass particles and silicate glass and thermally baking the coatingtogether with the substrate, or a step of thinly coating with anon-aqueous solution containing a material having a fluorocarbon groupand a chlorosilane group, or a step of coating with a solutioncontaining a material having a fluorocarbon group and an alkoxysilanegroup to produce a polymer film.

Also, there is provided a method of manufacturing a water- andoil-repelling coating film having surface irregularities comprising astep of coating a desirable substrate surface with a mixture of fineglass particles and silicate glass to produce a glass coating filmhaving desirable surface irregularities, a step of thermally baking thecoating together with the substrate and a step of causing chemicaladsorption to the substrate of a fluorocarbon silane-based surfaceactive material containing a chlorosilane group at one end to form amonomolecular adsorbed film.

More specifically, according to the invention there is provided a water-and oil-repelling coating film, in which a fluorocarbon-based polymerfilm is formed via an irregular surface film of a mixture of fineparticles and silicate glass, and which has desirable surfaceirregularities, and a method of manufacturing the same. Also provided isa water- and oil-repelling coating film, which comprises a coating layerof a mixture of fine glass particles and silicate glass and a chemicallyadsorbed monomolecular layer of a polymer material containing afluorocarbon group and a chlorosilane group, and which has desirablesurface irregularities, and a method of manufacturing the same.

The invention thus seeks to improve the performance of devices requiringheat-resistant, weather-resistant and wear-resistant coatings havingexcellent water- and oil-repelling properties. Such devices includeelectric products, vehicles and industrial apparatus.

Further, according to the invention a fluorine-containing chemicallyadsorbed monomolecular film is formed at least via siloxane bonds on thesurface of a substrate having surface irregularities less than thewavelength of visible light. It is thus possible to obtain a water- andoil-repelling coating film, which is excellent in luster and has anexcellent anti-contaminating effect such that contaminants will notattach without difficulty or will be readily removed if attached. Thatis, the film is a very thin chemically adsorbed monomolecular film, inwhich siloxane groups are chemically bonded to the substrate, the outerlayer of which has a portion containing fluorine groups. Thus, excellentluster and anti-contaminating effects can be obtained.

According to the invention, the substrate is made of a member of a groupconsisting of glass, ceramics, metals, stone, and plastics, hasexcellent anti-contaminating effects. These properties can be providedto articles in which it has been previously difficult to provideanti-contaminating effects thereto.

In a further aspect, usual glass, ceramic, stone, or metal products havehydrophilic surfaces containing hydroxyl groups. According to theinvention, there is provided a method of manufacture comprising a stepof contacting a product with an aqueous solution containing moleculeshaving a straight carbon chain having a chlorosilane at one end, e.g., achlorosilane-based surface active material with the molecules thereofhaving a fluorocarbon group and a chlorosilane group, to precipitate ofa monomolecular film of the material on the product surface through areaction brought about between hydroxyl groups of the product surfaceand chlorosilyl groups of the material or contacting the product with anon-aqueous solution containing a material with the molecules thereofhaving a plurality of chlorosilyl groups to precipitate the material onthe product surface through a reaction brought about between hydroxylgroups of the product surface and chlorosilyl groups of the material, astep of removing excess material with the molecules thereof having aplurality of chlorosilyl groups remaiming on the product surface bywashing with a non-aqueous organic solution, thereby forming asiloxane-based monomolecular film of the material with the moleculesthereof having a plurality of chlorosilyl groups on the substratesurface of the product, and a step of chemical adsorbing a silane-basedsurface active material with the molecules thereof containing a straightcarbon fluoride chain having a chlorosilane group at one end to form alamination chemically adsorbed monomolecular film. Thus, a laminationfluorocarbon chemically adsorbed monomolecular film may be formed on theproduct surface. In this case, by providing surface irregularities at alevel less than the visible light wavelength (under about 400 nanometer(nm), preferably from 10 to 300 nm (0.01 to 0.3 micron)) withoutspoiling the intrinsic luster of the product. Thus, it is possible toprovide a high performance product having high water- and oil-repellingeffects.

Further, according to the invention on a coarsened film is formed afluorine-containing chemically adsorbed monomolecular film via siloxanebonds. Thus, it is possible to obtain a water- and oil-repelling film,which includes a coating film having excellent water- and oil-repellingproperties as well as heat-, weather- and wear-resistant properties.

Further, according to the invention, the coarsened film has surfaceirregularities at a level less than 0.3 microns. In addition anexcellent light transmission property can be obtained, and the lighttransmission property of the film in the visible light range is nothindered.

Further, according to the invention, the material of the film is apoly(ethylene terephthalate) resin or a polyethylenetetrachloride resin.Thus materials which are suitable for cover films and protective filmscan be obtained.

The invention is applicable to various fields.

The invention can be widely applied to the following material surface.Materials made of metals, cermics or plastics, woods and stones etc. areapplicable to the substrate. The surface of the substrate can also becoated with paints or the like.

Examples of cutlery: a kitchen knife, scissors, a knife, a cutter, agraner, a razor, hair clippers, a saw, a plane, a chisel, a gimlet, abadkin, a bite (cutting tools), the edge of a drill, the edge of a mixerand juicer, a blade of a mill, a blade of a lawnmower, a punch, a strawcutter, a staple of a stapler, a can opener or a surgical knife and thelike.

Examples of needles: an acupuncture needle, a sewing needle, a mattingneedle, an injection needle, a surgical needle, a safety pin and thelike.

Examples of products in the pottery industry: products made of apottery, a glass, ceramics or enameled products. For example, such assanitary pottery (a chamber pot, a wash-bowl, a bathtub etc.), tableware(a rice-bowl teacup, a dish (plate), a bowl, a teacup, a glass, abottle, a coffee-pot (siphon), a pan, an earthenware mortar, a cup and(the like), vases (a flower bowl, a flowerpot, a bud vase and the like),water tanks (a breeding cistern, an aquarium water tank and the like),chemical experiment appliances (a beaker, a reactor vessel, a test tube,a flask, a laboratory dish, condenser, a mixing rod, stirrer, a mortar,a bat, a syringe etc.) a roof tile, enameled ware, an enameled washbowl,and an enameled pan and the like.

Examples of mirrors: a hand mirror, a full-length mirror, a bathroommirror, a lavatory mirror, vehicle mirrors (a rear-view mirror, a sidemirror, a door mirror etc.), half mirror, road mirrors such as a curvemirror, a show window glass, a salesroom in the department store,medical care mirrors, a concave mirror, a convex mirror and the like.

Examples of molding parts: dies for press molding, dies for castmolding, dies for injection molding, dies for transfer molding, dies forcompression molding, dies for transfer molding, dies for inflationmolding, dies for vacuum molding, dies for blow forming, dies forextrusion molding, dies for fiber spinning, a calender processing rolland the like.

Examples of ornaments: a watch, a jewel, a pearl, a sapphire, a ruby, anemerald, a garnet, a cat's eye, a diamond, a topaz, a bloodstone, anaquamarine, a turquoise, an agate, a marble, an amethyst, a cameo, anopal, a crystal, a glass, a ring, a bracelet, a brooch, a tiepin (astickpin), an earring, a necklace, jewelry made of platinum, gold,silver, copper, aluminium, titanium, tin and those alloy, stainlesssteel, a glass frame and the like.

Examples of forming molds for food: cake, cookies, bread-baking,chocolate, jelly, ice cream, ovenware, ice trays and the like.

Examples of cookware: kitchen utensils (a pan and a pot), a kettle, apot, a frying-pan, a hot plate, a toasting net, a takoyaki plate and thelike.

Examples of papers: photogravure paper, hydrophobic and oilphobic paper,poster paper, high-grade pamphlet paper, wrapping paper, package paper,drinking package paper, container paper, printing paper, syntheticinsulating paper and the like.

Examples of resin(s): a polyolefin such as a polypropylene andpolyethylene, a polyvinylchloride plastic, a polyamide, a polyimide, apolyamideimide, a polyester, an aromatic polyester, a polycarbonate, apolystyrene, a polysulfide, a polysulfone, a polyethersulfone, apolyphenylenesulfide, a phenolic resin, a furan resin, a urea, an epoxyresin, a polyurethane, a silicon resin, an ABS resin, a methacrylicresin, an acrylate resin, a polyacetal, a polyphenylene oxide, apolymethylpentene, a melamine resin, an alkyd resin, an unsaturatedpolyester resin and the like.

Examples of rubber: styrene-butadiene rubber, butyl rubber, nitrilrubber, chloroprene rubber, polyurethane rubber, silicon rubber and thelike.

Examples of household electrical appliances: a television, a radio, atape recorder, an audio device, a compact disc (CD) device, arefrigerator, a freezer, an air conditioner, a juicer, a mixer, a bladeof an electric fan, a lighting apparatus, a dial plate, a dryer forperms and the like.

Examples of sports articles: skis, fishing rods, poles for polevaulting, boats, yachts, surfboards, golf balls, bowling balls, fishingline, fishing nets, floats and the like.

The examples applying to vehicle parts:

(1) ABS resin: a lamp cover, an instrument panel, trimming parts, aprotector for a motorcycle.

(2) Cellulose plastic: a car mark, a steering wheel

(3) FRP (fiber reinforced plastics): a bumper, an engine cover (jacket)

(4) Phenolic resin: a brake

(5) Polyacetal: wiper gear, a gas valve

(6) Polyamide: a radiator fan

(7) Polyarylate (polycondensation polymerization by bisphenol A andpseudo phtalic acid): a directional indicator lamp or lens, a cowl boardlens, a relay case

(8) Polybutylene terephthlate (PBT): a rear end, a front fender

(9) Poly(amino-bismaleimide): engine parts, a gear box, a wheel, asuspension drive system

(10) Methacrylate resin: a lamp cover lens, a meter panel and its cover,center mark

(11) Polypropylene: a bumper

(12) Polyphenylene oxide: a radiator grill, a wheel cap

(13) polyurethane: a bumper, a fender, an instrument panel, a fan

(14) Unsaturated polyester resin: a body, a fuel, tank, a heaterhousing, a meter pannel.

Examples of office supplies: a fountain pen, a ball-point pen, apropelling pencil (an automatic or a mechanical pencil), a pencil case,a binder, a desk, a chair, a bookshelf, a rack, a telephone stand table,a rule (measure), a drawing instrument and the like.

Examples of building materials: materials for a roof, an outer wall andinteriors. Roof materials such as a brick, a slate and a tin (agalvanized iron sheet) and the like. Outer wall materials such as wood(including a processed manufactured wood), mortar, concrete, ceramicssizing, a metalic sizing, a brick, a stone, plastics and a metal such asaluminium. Interior materials such as a wood (including processed wood),a metal such as aluminium, plastics, paper, fiber and the like.

Examples of building stones: granite, marble and others used for such asa building, a building material, an architectural fixture, an ornament,a bath, a grave, a monument, a gatepost, a stone wall, a paving stoneand the like.

Examples of musical instruments and sound apparatus: a percussioninstrument, a stringed instrument, a keyboard instrument, a woodwindinstrument, brass and others, and sound apparatus such as a microphoneand a speaker. To be specific, there are musical instruments such as adrum, a cymbal, a violin, a cello, a guitar, a koto (harp), a piano, aflute, a clarinet, a bamboo flute and a horn, and sound apparatus suchas a microphone, a speaker and an ear-phone and the like.

Examples of a thermos bottle, a vacuum bottle, a vacuum vessel and thelike.

Examples of a highly resisiting voltage insulator such as a powersupplying insulator or a spark plug, which are highly hydrophobic,oilphobic and aid in preventing contamination.

Now, examples of the invention will be given which are not to beconstructed as limiting the invention in any way. Unless otherwisespecified, % is by weight in the examples.

EXAMPLE 1

As shown in FIG. 1, a hydrophilic substrate 1 was prepared, thesubstrate being of such material as glass, ceramics or metals, e.g., Aland Cu. If a substrate made of a plastic or like material and having nosurface oxide film is to be used, its surface may be preliminarily madehydrophilic. That is, hydroxyl groups may be introduced to its surfaceby treating the surface in an oxygen-containing plasma or coronatreatment atmosphere at 100 W for 20 minutes. Then, the substratesurface may be coated with a solution containing 90% of normalhexadecane and 10% of chloroforms, the solution being prepared bydissolving, to a concentration of several %, a non-aqueous solutioncontaining a mixture of a material with the molecules thereof containinga fluorocarbon group and a chlorosilane group such as

    CF.sub.3 --(CF.sub.2).sub.5 (CH.sub.2).sub.2 SiCl.sub.3

hydrophilic silica fine surface particles 2 with the molecules thereofcontaining an -OH group (FIG. 2). The coating was then baked in amoisture-containing atmosphere at 200° C. for about 30 minutes. Sincethe hydrophilic fine surface particles had --OH groups exposed on thesurface, a hydrochloric acid removal reaction (dehydrochlorinationreaction) was brought about between chlorosilyl groups of thefluorine-containing chlorosilane-based surface active material and --OHgroups, thus producing --Si(O--)₃ bonds on the surface. Afluorine-containing siloxane fluorocarbon-based polymer film 3 thus wasformed which was chemically bonded to the surfaces of the substrate andthe fine particles (FIG. 3).

As another example, by dissolving or suspending

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 SiCl.sub.3

to a concentration of 1% and hydrophilic fine surface silica particleswith the molecule thereof containing an --OH group to a concentration ofabout 10%, a solution or suspension containing 80%, n-hexadecane and 12%of carbon tetrachloride and 8% of chloroform was obtained, which wasthen coated on the surface of the afore-mentioned substrate providedwith a surface polysiloxane coating film having numerous --SiOH bondsand baked in a moisture-containing atmosphere at 200° C. for about 30minutes, thus producing bonds of

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 Si(O--).sub.3

A fluorocarbon-based coating film 3 was thus obtained, which had surfaceirregularities of 0.5 to 50 microns (μm) meter, preferably 1 to 10microns (μm), and a thickness of 1 to 5 microns (FIG. 4). FIG. 3 shows aportion A of FIG. 4 to an enlarged scale. This coating film did notseparate in a checkerboard test.

Further, by adding SiX_(s) Cl_(4-s) where X represents a hydrogen atomor a substitute group such as an alkyl group, and s represents 0, 1, or2, for example by 3% by weight SiCl₄ as a crosslinking agent for thematerial with the molecules thereof containing a fluorocarbon group anda chlorosilane group, to the solution containing the material, the bondsof

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 Si(O--).sub.3

were crosslinked three-dimensionally via bonds of --Si(O--)₃. Afluorocarbon-based coating film was thus obtained, which had aboutdouble the hardness of a film obtained without addition of SiCl₄.

The fluorocarbon-based coating film was thus produced having surfaceirregularities of about 10 microns and a water wetting angle of about130 to 140 degrees.

Although the above example used CF₃ --(CF₂)₅ (CH₂)SiCl₃, and CF₃ CH₂O(CH₂)₁₅ SiCl₃ as the crosslinking agents, if an ethylene group oracethylene group is added to or incorporated in the alkyl chain portion,crosslinking can be obtained by irradiating the coating film with anelectron beam of about 5 Mrads. It is thus possible to readily obtain acoating film with the hardness increased by about ten times. In additionto the above fluorocarbon-based surface active material may be used

CF₃ (CH₂)₂ Si(CH₃)₂ (CH₂)₁₅ SiCl₃, CF₃ (CF₂)₃ (CH₂)₂ Si(CH₃)₂ (CH₂)₉SiCl₃, and CF₃ COO(CH₂)₁₅ SiCl₃.

EXAMPLE 2

As shown in FIG. 5, like Example 1, a hydrophilic substrate 11 wascoated with an alcohol solution containing a material with the moleculesthereof having a fluorcarbon group and an alkoxysilane group, forexample

    CF.sub.3 --(CF.sub.2).sub.5 (CH.sub.2).sub.2 Si(OC.sub.2 H.sub.5).sub.3

The coating was baked at 200° C. for about 30 minutes. Since thesubstrate 11 and hydrophilic surface fine particles 12 had --OH groupsexposed on their surfaces, an alcohol removal reaction (dealcoholationreaction) was brought about between the alkoxy groups of thefluorine-containing alkoxysilane-based surface active material and -OHgroups, thus producing --Si(O--)₃ bonds on the substrate surface. Afluorine-containing siloxane fluorocarbon-based polymer film 13 thuscould be formed on the surface of the substrate and the fine particleswhich were chemically bonded to the substrate (FIG. 7).

As another an example, by dipping the substrate surface with an ethanolsolution or suspension prepared by dissolving or suspending 1% of

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 Si(OCH.sub.3).sub.3

and about 10% of hydrophilic surface silica fine particles having adiameter of 0.5 to 50 microns, preferably 1 to 10 microns, andcontaining an --OH group and baking the coating at 200° C. for about 30minutes, bonds of

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 Si(O--).sub.3

were produced. Thus, a fluorocarbon-based coating film 13 with surfaceirregularties of 0.5 to 50 microns, preferably 1 to 10 microns, andhaving a thickness of 1 to 5 microns could be produced (FIG. 8). FIG. 7shows an enlarged scale of a portion B shown in FIG. 8. This coatingfilm did not separate in a checkerboard test.

Further, by adding Si(OCH₃)₄ about 5% by weight as a crosslinking agentfor the material having a fluorocarbon group and an alkoxysilane groupto solution containing the material, the bonds of CF₃ CH₂ O(CH₂)₁₅Si(O--)₃ were crosslinked three-dimensionally via --Si(O--)₃ bonds. Afluorocarbon-based coating film was obtained, which had about 2 to 2.5times the hardness of the film obtained without addition of Si(OCH₃)₄.

The fluorocarbon-based coating film was thus produced having surfaceirregularities of about 10 microns and a water contact angle of about135 to 140 degrees.

Further, by adding 10% of Si(OC₃ H₇)₄ as a crosslinking agent for thematerial containing a fluorocarbon group and an alkoxysilane group tothe solution containing the material, a fluorocarbon-based coating filmhaving about four times the hardness could be obtained.

Further by carrying out the coating with a non-aqueous solutioncontaining the material having a fluorocarbon group and an alkoxysilanegroup, to which 20 wt. % of fine particles of a fluorocarbon-basedpolymer (i.e., polyethylene-tetrafluoride) was further dispersed, afluorocarbon-based coating film could be obtained, which had excellentadhesion compared to the prior art although the hardness was comparableto the prior art.

While the above example used

    CF.sub.3 --(CF.sub.2).sub.5 (CH.sub.2)Si(OC.sub.2 H.sub.5).sub.3 or CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 Si(OCH.sub.3).sub.3

as the crosslinking agent, by adding or incorporating an ethylene groupor an acetylene group into the alkyl chain portion, the resultingcoating film can be subjected to crosslinking with irradiation by anelectron beam of about 5 Mrads. It is thus possible to obtain a coatingfilm having about 10 times the hardness.

Further, as the fluorocarbon-based surface active material other thannoted above could be utilized

CF₃ (CH₂)₂ Si(CH₃)₂ (CH₂)₁₅ Si(OCH₃)₃, CF₃ (CF₂)₃ (CH₂)₂ Si(CH₃)₂ (CH₂)₉Si(OCH₃)₃, and CF₃ COO(CH₂)₁₅ Si(OC₂ H₅)₃ etc.

EXAMPLE 3

As shown in FIG. 9, a hydrophilic substrate 21 was prepared, thesubstrate being of such material as glass, ceramics or metals, e.g., Aland Cu. If a substrate made of a plastic or like material and having nosurface oxide film is to be used, its surface may be preliminarily madehydrophilic. That is, hydroxyl groups were introduced to its surface, bytearing the surface in an oxygen-containing plasma atmosphere at 100 Wfor 20 minutes. Then, the substrate surface was coated with anon-aqueous solution containing a material containing a plurality ofchlorosilyl groups (e.g., SiCl₄, SiHCl₃, SiH₂ Cl₂, and Cl(SiCl₂ O)₂SiCl₃ (n represents an integer), particularly Cl(SiCl₂ O)₂ SiCl₃ greatlyeffective for making the surface hydrophilic, the solution beingprepared by dissolving, for instance, 1% by weight of the material inchloroform solvent.

As an example, by using Cl(SiCl₂ O)₂ SiCl₃ as the material containing aplurality of chlorosilyl groups, since the surface of the substrate 21contained hydrophilic --OH groups, a dehydrochlorination reaction wasbrought about on the surface, and molecules represented by formula [1]:##STR1## were formed by --SiO-- bonds to the substrate surface.

By subsequently drying the coating in a moisture-containing atmosphere adehydrochlorination reaction occurred between --Cl groups remainingwithout reaction with the substrate and water. Thus, a coating film 22of polysiloxane was formed, as shown in FIG. 10. The coating film thusformed bonded to the substrate surface by chemical bonds of --SiO--. Thesurface of the siloxane coating film had numerous --SiOH bonds.

Subsequently, further coating was done using a non-aqueous solutioncontaining a mixture of fine particles and a material containing afluorocarbon group and a chlorosilane group, for example a solutionobtained by dissolving

    CF.sub.3 --(CF.sub.2).sub.7 (CH.sub.2).sub.2 SiCl.sub.3

to a concentration of 2.0% in a solvent containing 90% of n-hexadecaneand 10% of chloroform (FIG. 11). The coating was baked at 200° C. forabout 30 minutes. Since the polysiloxane coating film and hydrophilicfine surface particles have --OH groups exposed on their surfaces, adehydrochlorination reaction was brought about between chlorosilylgroups of the fluorine-containing chlorosilane surface active materialand the --OH groups. A fluorine-containing siloxane fluorocarbon-basedpolymer film 23 was thus chemically bonded to the inner polysiloxanecoating film and the fine particles (FIG. 12).

As another an example, by preparing a solution containing 80% ofn-hexadecane, 12% of carbon tetrachloride and 8% of chloroform bydissolving 1% of

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 SiCl.sub.3

and silica fine particles 24 with a diameter of 0.5 to 50 microns,preferably 1 to 10 microns, and containing hydrophilic --OH groups onthe surface to a concentration of about 10%, coating on the substratesurface formed with the polysiloxane adsorbing film containing many--SiOH bonds and baking the coating in a moisture-containing atmosphereat 200° C. for about 30 minutes, bonds of

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 Si(O--).sub.3

were produced. Thus, a fluorocarbon-based coating film having surfaceirregularities of 0.5 to 50 microns, preferably 1 to 20 microns, andhaving a thickness of 1 to 5 microns could be obtained (FIG. 13). Thiscoating film did not separate in a checkerboard test.

Further, by adding for example by 3% SiCl₄, as a crosslinking agent forthe material having a fluorocarbon group and a chlorosilane group, tothe solution containing the material, the bonds of

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 Si(O--).sub.3

are crosslinked three-dimensionally via --Si(O--)₃ bonds. Thus, afluorocarbon-based coating film was obtained, which had about double thehardness of the coating film without the addition of SiCl₄.

The fluorocarbon-based coating film thus produced had surfaceirregularities of about 10 microns and had a water wetting angle ofabout 140 to 150 degrees.

The hydrophilic substrate 27 (FIG. 14) was dipped into a non-aqueoussolution, for example a chloroform solution, containing a materialhaving a plurality of chlorosilyl groups for about one hour. Because ofthe presence of hydrophilic -OH groups on the surface of the substrate27, a dehydrochlorination reaction was brought about on the surface.Thus, molecules represented above by formula [1] were adsorbed to thesubstrate surface.

By subsequently washing with a non-aqueous solution, for examplechloroform, non-reacted materials were washed away. Following washingwith water, a chemically adsorbed monomolecular film of polysiloxanerepresented by the formula [2]; ##STR2## could be obtained on thesubstrate surface (FIG. 15).

The monomolecular film 25 thus produced is bonded by chemical bonds(i.e., covalent bonds) of --SiO-- to the substrate, and thus isdifficult to separate. It has numerous --SiOH bonds on its surface.

As a further example, a non-aqueous solution containing a materialhaving a fluorocarbon group and a chlorosilane group and hydrophilicfine surface particles was prepared. For example a solution containing80 % of n-hexadecane, 12% of carbon tetrachloride and 8% of chloroformwas prepared by dissolving 1% of

    CF.sub.3 --(CF.sub.2).sub.7 (CH.sub.2).sub.2 SiCl.sub.3

and about 10% of fine particles 24 of silica with a diameter of 0.5 to50 microns, preferably 1 to 10 microns, and with the surface containinghydrophilic --OH groups. This solution was coated on the substrateprovided with the monomolecular film having many --SiOH bonds on thesurface and baked in a moisture-containing atmosphere at 200° C. for 30minutes. As a result, bonds of

    CF.sub.3 --(CF.sub.2).sub.7 (CH.sub.2).sub.2 Si(O--).sub.3

were produced (FIG. 16). A fluorocarbon-based coating film 26 havingsurface irregularities of 0.5 to 50 microns, preferably 1 to 10 microns,having a thickness of 1 to 20 microns and containing fine particlescould be formed which are bonded to the inner polysiloxane monomolecularfilm (FIG. 17). This coating film was difficult to separate in acheckerboard test.

Further, by adding 15% by weight of SiCl₄ as a crosslinking agent forthe material having a fluorocarbon group and a chlorosilane group to thesolution containing the material, a fluorocarbon-based coating filmhaving about five times the hardness, could be obtained.

Further, by carrying out the coating with a non-aqueous solutioncontaiing a material having a fluorocarbon group and a chlorosilanegroup, to which about 20 wt. % of fine particles of fluorocarbon-basedpolymer (i.e., ethylene polytetrafluoride) was further dispersed, afluorocarbon-based coating film with surface irregularities could beobtained, which had excellent adhesion compared to that in the prior artalthough the hardness was comparable thereto.

By adding or incorporating an ethylene group or an acetylene group to orinto alkyl chain portion, crosslinking is obtained by irradiation withan electron beam of about 5 Mrads. after the formation of the coatingfilm. A coating film having about 10 times the hardness is obtained.

EXAMPLE 4

As in the case of example 3, a hydrophilic substrate 31 as shown in FIG.19 was dipped and held in a non-aqueous solution containing a materialhaving a plurality of chlorosilyl groups and then removed. Since thesurface of the substrate 31 had hydrophilic --OH groups, adehydrochlorination reaction was brought about on the surface, andmolecules as represented: Cl(SiCl₂ O)₂ SiCl₃ were secured by --SiO--bonds to the substrate such as above formulas [1] to [2].

By subsequently drying the system in a moisture-containing atmosphere, acoating film 32 (FIG. 20) of polysiloxane could be obtained through adehydrochlorination reaction brought about between unreacted --Cl groupsand water. The coating film of polysiloxane thus obtained was coupled tothe substrate surface by chemical bonds of --SiO-- and was difficult toseparate. It had numerous --SiO-- bonds on the surface.

As a further example, an alcohol solution containing a material having afluorocarbon group and an alkoxysilane group and fine particlescontaining hydrophilic --OH groups on the surface was prepared. Forexample, by coating an ethanol solution obtained by dissolving 1% of

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 Si(OCH.sub.3).sub.3

and about 10% of fine particles 34 of silica with a diameter of 0.5 to50 microns, preferably 1 to 10 microns, and having hydrophilic --OHgroups on the surface (FIG. 21), on the substrate provided with thepolysiloxane coating film having numerous --SiOH bonds on the surfaceand baking the coating at 200° C. for about 30 minutes, bonds of

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 Si(O--).sub.3

were produced. A fluorocarbon-based coating film having surfaceirregularities of 0.5 to 50 microns (μm), preferably 1 to 10 microns,and a thickness of 1 to 5 microns were obtained (FIG. 22 and 23). Thiscoating film 33 did not separate in a checkerboard test.

Further, by adding for example by 5% by weight Si(OCH₃)₄, as acrosslinking agent for the material having a fluorocarbon group and analkoxysilane group to the solution containing the material, the bonds of

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 Si(O--).sub.3

were crosslinked three-dimensionally by --Si(O--)₃ . Afluorocarbon-based coating film was thus obtained, which had aboutdouble the hardness of a coating film obtained without addition ofSi(OCH₃)₄.

The fluorocarbon-based coating film thus obtained had surfaceirregularities of about 10 microns, and had a water contact angle ofabout 135 to 140 degrees.

Further, the hydrophilic substrate 37 (FIG. 24) was dipped and held in anon-aqueous solution containing a material having a plurality ofchlorosilyl groups (for example the solution was obtained by dissolving1% by weight of the material in chloroform solvent).

With Cl--(SiCl₂ O)₂ --SiCl₃ used as the material having a plurality ofchlorosilyl groups, for example, a dehydrochlorination reaction wasbrought about on the surface because of the presence of hydrophilic OHgroups on the surface of the substrate 37, and the molecules representedabove by formula [1] were adsorbed to the substrate surface.

By subsequently washing the substrate with a non-aqueous solvent, forexample chloroform, and then with water, unreacted molecules wereremoved, thus obtaining a polysiloxane monomolecular film 35 representedabove by formula [2] (FIG. 25).

The monomolecular film 15 thus obtained was perfectly bonded to thesubstrate via chemical bonds of --SiO-- and were difficult to separate.Its surface had numerous --SiO-- bonds.

As a further example, a solution containing a material having afluorocarbon-based group and an alkoxysilane group and fine particleswith a hydrophilic surface was prepared. For example, a methanolsolution containing 1% of

    CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 Si(OC.sub.2 H.sub.5).sub.3

and about 10% of fine particles 34 of silica with a diameter of 0.5 to50 microns, preferably 1 to 10 microns and containing hydrophilic --OHgroups on the surface was prepared. The solution was coated on thesubstrate provided with the monomolecular film having numerous --SiOHgroups on the surface (FIG. 26) and baked at 200° C. for about 30minutes, thus producing CF₃ (CF₂)₇ (CH₂)₂ Si(O--)₃ bonds. Afluorocarbon-based coating film 36 with surface irregularities of 0.5 to50 microns, preferably 1 to 10 microns, was formed (FIGS. 27 and 28).This coating film 36 was chemically bonded to the inner polysiloxanemonomolecular film and did not separate in a checkerboard test. Further,by adding 10% as a crosslinking agent for the material containing afluorocarbon group and an alkoxysilane group to the solution containingthe material, a fluorocarbon-based coating film having about four timesthe hardness was obtained.

Similar coating was carried out by further dispersion adding 20% of fineparticles of fluorocarbon-based polymer (i.e., polyethylenetetrafluoride) to the non-aqueous solution containing the materialhaving a fluorocarbon group and an alkoxysilane group, afluorocarbon-based coating film could be obtained, which had excellentadhesion compared to the prior art although the hardness was comparable.

In the above example, by adding or incorporating an ethylene group oracetylene group into the alkyl chain portion, the coating film can becrosslinked after formation thereof by irradiating it with an electronbeam of about 5 Mrads. Thus, a coating film which was about 10 times ashard could be readily obtained.

In the above example, after processing the substrate surface with acompound having a chlorosilyl group, a polysiloxane film is formed. Onthis film is formed a thin film chemically bonded to the substratesurface by using as a compound having a fluorocarbon group and asiloxane group, for example a surface active material containing achlorosilane compound and an alkylsilane compound, and reacting thematerial with --OH groups on the surface. At this time, hydrophilic fineparticles are provided to increase adhesion. By so doing, an excellentwater- and oil-repelling and durable fluorine-containing coating film issatisfactorily adhered to the substrate.

EXAMPLE 5

As shown in FIG. 29, a hydrophilic substrate 41, for example a substrateof glass or a ceramic material or a metal such as Al or Cu or a plasticsubstrate with the surface thereof rendered to be hydrophilic, isprepared. When a plastic substrate without any oxide film on the surfaceis to be used, the surface may be made hydrophilic, i.e., hydroxylgroups were introduced into the surface, in advance by treating thesurface in an oxygen-containing plasma atmosphere at 100 W for 20minutes. Then, the substrate surface is coated by a casting process witha mixture containing, in a ratio of about 1:1, fine particles 42 ofsilica with a diameter of 1 to 20 microns, preferably about 10 microns,for example, "Microsheargel DF10-60A" or "-120A" by Asahi Glass Co.,Ltd., and silicate glass, "Hard Coating Agent KP-1100A" or "-1100B" byShinetsu Kagaku Kogyo Co., Ltd. or "Si-80000" by Tokyo Ohka Kogyo Co.,Ltd. The coating is then thermally treated at 500° C. for 30 minutes orsubjected to plasma ashing at 300 W for about 20 minutes. As a result, aglass layer 43 with surface irregularities on the micron level can beformed on the substrate surface. Then, coating is carried out with anon-aqueous solution containing a material having a fluorocarbon groupand a chlorosilane group, for example a solution obtained by dissolvingseveral per cent of

    CF.sub.3 --(CF.sub.2).sub.n --R--SiX.sub.p Cl.sub.3-p

where n, R, X and p are as noted above in a solution containing 90% ofnormal hexadecane and 10% of chloroform, followed by baking in amoisture-containing atmosphere at 200° C. for about 30 minutes. As aresult, --OH groups are exposed on the surface of the glass layer 43,and a hydrochloric acid reaction is brought about between thechlorosilyl groups of the fluorine-containing chlorosilane-based surfaceactive agent and the --OH groups, thus producing bonds of --Si(O--)₃ onthe surface. A fluorine-containing siloxane fluorocarbon-based polymerfilm 44 is formed on the glass layer, which has surface irregularitieson the micron level, such that it is chemically bonded to the glasslayer surface (FIG. 30).

As an example, by dip coating the surface of a glass substrate using"DF10-60A" having a diameter of about 10 microns as the fine particlesand "KP-1100A" as the silicate glass, followed by thermal treatment(i.e., baking) at 350° C. a glass layer with surface irregularities ofabout 10 microns could be obtained. Subsequently, the substrate providedwith the polysiloxane coating film having numerous --SiOH groups on thesurface was coated with a solution containing 80% of n-hexadecane, 12%of carbon tetrachloride and 8% of chloroform into which about 1% byweight of CF₃ CH₂ O(CH₂)₁₅ SiCl₃ was dissolved. After coating, thesubstrate was baked in a moisture-containing atmosphere at 200° C. for30 minutes, thus producing bonds of

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 Si(O--).sub.3

Thus, a fluorocarbon-based coating film 44 with surface irregularitiesof about 10 microns and having a thickness of 1 to 5 microns, wasobtained (FIG. 30 and 32). This coating film did not separate in acheckerboard test.

In this case, by adding as a crosslinking agent for the material havinga fluorocarbon group and a chlorosilane group 3% by weight SiCl₄ to thesolution containing the material, a fluorocarbon-based coating filmhaving about double the hardness was obtained.

This fluorocarbon-based coating film had surface irregularities of about10 microns and a water contact angle of about 130 to 140 degrees. Thewater contacting is shown in FIG. 31.

EXAMPLE 6

As in the preceding Example 5, a glass layer having surfaceirregularities is formed on a substrate as shown in FIG. 29, and thencoated with an alcohol solution containing a material having afluorocarbon group and an alkoxysilane group, for example a solutionobtained by dissolving several per cent of CF₃ --(CF₂)_(n) --R--SiY_(q)(OA)_(3-q)

where n represents O or an integer, R represents an alkyl group, anethylene group, an acetylene group or a substituted group containing asilicon or hydrogen atom, Y represents a substituted group such as analkyl group, and OA represents an alkoxy group (A representing ahydrogen atom or an alkyl group), in methanol, followed by baking at200° C. for about 30 minutes. An alcohol elimination reaction(dealcoholation) is thus brought about between alkoxyl groups in thefluorine-containing alkoxysilane-based surface active agent and the --OHgroups exposed at the surface of the glass layer 43, thus producing--Si(O--)₃ bonds on the surface. Thus, as in Example 5, afluorine-containing siloxane fluorocarbon-based polymer film is formedon the irregular surface of the glass layer.

As an example, an ethanol solution was prepared by dissolving about 1%of

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 Si(OCH.sub.3).sub.3

and coated on the substrate provided with the polysiloxane coating filmhaving many surface --SiOH bonds, followed by

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 Si(O--).sub.3

baking at 200° C. for about 30 minutes. A fluorocarbon-based polymerfilm with surface irregularities of about 10 microns and having athickness of 1 to 5 microns was thus obtained (FIG. 30). This coatingfilm did not separate in a checkerboard test.

By adding, as a crosslinking agent for the material containing afluorocarbon group and an alkoxysilane group 5% by weight Si(OCH₃)₄ tothe solution containing the material, bonds of CF₃ CH₂ O(CH₂)₁₅ Si(O--)₃were crosslinked three-dimensionally via bonds of --Si(O--)₃ . Afluorocarbon-based polymer film was obtained which had about 2 to 2.5times the hardness of a film obtained without use of Si(OCH₃)₄.

When water drops 45 were caused to fall onto this fluorocarbon-basedpolymer film with surface irregularities of about 10 microns, theycontacted the film only at raised portions. Thus, the film was highlywater-repelling, as shown in FIG. 31, and its water contact angle wasabout 135 to 140 degrees.

By adding about 10% by weight of Si(OC₃ H₇)₄ as a crosslinking agent forthe material containing a fluorocarbon group and an alkoxysilane groupto the solution containing the material, a fluorocarbon-based polymerfilm having about four times the hardness was obtained.

When similar coating was carried out using the non-aqueous solutioncontaining a material containing a fluorocarbon group and analkoxysilane group, to which was added 20% of fine particles offluorocarbon-based polymer (i.e., polyethylenetetrafluoride), afluorocarbon-based polymer film was obtained, which had excellentadhesion was highly water- and oil-repelling although hardness was suchas that obtainable in the prior art.

By adding or incorporating an ethylene group or acetylene group into thealkyl chain portion, the coating film was crosslinked by irradiating itwith an electron beam of about 5 Mrads. A coating film having about 10times the hardness was readily obtained.

EXAMPLE 7

As in the previous Example 5, a glass layer having surfaceirregularities was formed on a glass substrate as shown in FIG. 29.Then, the substrate, being provided with the monomolecular film havingnumerous surface --SiOH bonds, was dipped for about 30 minutes in anon-aqueous solution and held. The solution contained a material havinga fluorocarbon group and a chlorosilane group. For example a solutionobtained by dissolving about 1% of CF₂ (CF₂)₇ (CH₂)₂ SiCl₃ in a solutioncontaining 80% of n-hexadecane, 12% of carbon tetrachloride and 8% ofchloroform. As a result, bonds of

    CF.sub.2 (CF.sub.2).sub.7 (CH.sub.2).sub.2 Si(O--).sub.3

were formed on the substrate surface, thus forming a fluorine-containingwater- and oil-repelling film 44 (i.e., chemically adsorbedmonomolecular film) such that it was chemically bonded to the glasslayer and had desirable surface irregularities (FIG. 30). This water-and oil-repelling film 44 (or monomolecular film) did not separate in acheckerboard test. In addition, since the fluorocarbon groups were atthe surface, the surface energy was very low, and the water contactangle was 135 to 240 degrees.

By adding or incorporating an ethylene group or acethylene group intothe alkyl chain portion, the monomolecular film was crosslinked afterformation by irradiation with an electron beam of about 5 Mrads. Thehardness was further improved.

EXAMPLE 8

A processed glass plate was prepared. After washing with an organicsolution, its surface was coarsened by sand blasting to form surfaceirregularities on a sub-micron order of 0.1 to 1.0 microns, for example0.4 to 0.9 microns. The surface irregularities may also be formed by achemical etching process using fluorine oxide or a rubbing process usingsand paper. Subsequently, the glass plate was dipped and held for about2 hours in a non-aqueous solution containing a material having afluorocarbon chain group and a chlorosilane group. For example asolution was obtained by dissolving 1% by weight of

    CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2)SiCl.sub.3

into a solution containing 80 % of n-hexadecane (or toluene, xylene ordicyclohexyl), 12% of carbon tetrachloride and 8% of chloroform. As aresult, a hydrochloric acid removal reaction (dehydrochlorination) wasbrought about between the --SiCl groups of the material containing afluorocarbon group and a chlorosilane group and the hydroxyl groupscontained in the surface of natural oxide film formed on the glass platesurface, thus producing bonds of

    CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2)Si(O--).sub.3

over the entire glass plate surface. Thus, a fluorine-containingmonomolecular film was formed which was chemically bonded to the glassplate surface and had a thickness of about 15 angstroms. Thismonomolecular film was chemically bonded and difficult to separate. Witha glass plate comprising a plastic material such as an acrylate resin ora polycarbonate resin, the same technique could be used by oxidizing thecoarsened surface to be hydrophilic by a plasma process at 300 W forabout 10 minutes and using a freon solvent in lieu of the surface activematerial.

The processed glass plate was trial used to find that the attachment ofcontaminants could be greatly reduced compared to a glass plate whichwas not processed. Contaminants that were attached could be readilyremoved by rubbing the glass plate with a brush. At this time, no scaror scratch was produced. Further, oily fat contaminants could be removedby merely water washing. The wetting property with respect to water issimilar to that of lotus leaves, and the contact angle was 155 degrees.

EXAMPLE 9

With an aluminum plate, which contains less hydroxyl groups although itremains hydrophilic, surface irregularities of about 0.5 to 0.8 micronare formed by electrolytic etching.

Surface irregularities may also be formed by a chemical etching processusing fluorine oxide, a plasma spattering process carried out in vacuumor a rubbing process using sand paper. Metal substrates may all besimilarly treated. With a substrate of a plastic material such as anacrylate resin or a polycarbonate resin, the same technique is usedafter coarsening the surface and then oxidizing the surface to behydrophilic by a plasma process carried out at 200 W for about 10minutes.

Then, the plate is dipped and held for about 30 minutes in a non-aqueoussolution containing a material having a plurality of chlorosilyl groups.For example, a solution was obtained by dissolving 1% by weight of SiCl₄in a chloroform solvent, and a hydrochloric acid removal reaction wasbrought about owing to the --OH groups present to a certain extent atthe aluminum plate surface. A chlorosilane monomolecular film of thematerial containing a plurality of chlorosilyl groups was formed.

For example, by using SiCl₄ as the material containing a plurality ofchlorosilyl groups, a dehydrochlorination reaction is brought aboutowing to the hydrophilic --OH groups exposed at the aluminum platesurface, and molecules of Cl₃ SiO-- or Cl₂ Si(O--)₂ are secured to thesurface by --SiO-- bonds.

By subsequently washing the system with a non-aqueous solvent, e.g.,chloroform, and then with water, unreacted SiCl₄ molecules are removedfrom the aluminum plate to obtain a siloxane monomolecular film of (OH)₃SiO-- or (OH)₂ Si(O--)₂ on the aluminum plate surface.

The monomolecular film thus obtained is perfectly bonded to the aluminumplate 46 by chemical bonds of --SiO-- and did not separate. In addition,its surface has numerous -SiOH (or silanol) bonds. Further, hydroxylgroups corresponding in number to about three times the initial numberare produced.

As an example, the aluminum plate 46, provided with a monomolecular filmhaving numerous surface --SiOH bonds, was dipped and held for about onehour in a non-aqueous solution containing a material containing a carbonfluoride group and a chlorosilane group. For example a solution wasobtained by dissolving about 1% of CF₃ (CF₂)₇ (CH₂)SiCl₃ in a solutioncontaining 80% of n-hexadecane, 12% of carbon tetrachloride and 8 % ofchlorofrom. As a result, bonds of

    CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2)Si(O--).sub.3

were formed on the aluminum plate surface. A fluorine-containingmonomolecular film 48 was formed over the entire aluminum plate 46surface. The film was chemically bonded (i.e., covalently bonded) to theinner siloxane monomolecular film 47 and had a thickness of about 15angstroms (1.5 nm). I t did not separated in a checkerboard test. Itswater contact angle was about 155 degrees.

Further, using a glass plate in lieu of the aluminum plate in the aboveExample 8, on the surface desired to remain hydrophilic (for example theinner surface) was formed a hydrophilic coating film insoluble in anorganic solvent (for example by coating an aqueous solution ofpolyvinylalcohol (poval) to a thickness of several microns) for thepurpose of imparting an anti-fogging effect before carrying out chemicaladsorption of the material containing a carbon fluoride group and achlorosilane group. After the chemical adsorption, the hydrophiliccoating film was removed by water washing, thus obtaining a glass plateprovided with a monomolecular film (or siloxane film), which had awater- and oil-repelling contamination free outer layer and hydrophilichydroxyl groups present at the inner surface. The anti-fogging effect ofthis glass plate was tested to find that its surface was lefthydrophilic and could be readily wetted by water and would not fog.

By carrying out the chemical adsoprtion using a mixture of two differentsurface active materials with different molecular lengths, for exampleCF₃ (CF₂)₇ (CH₂)₂ Si(CH₃)₂ (CH₂)₉ SiCl₃ and CF₃ (CF₂)₇ (CH₂)₂ Si(CH₃)₂(CH₂)₆ SiCl₃ or CF₃ (CF₂)₇ (CH₂)₂ SiCl₃ and CF₃ (CF₂)₅ (CH₂)₂ SiCl₃ themixture being in a ratio of about 3:1 to 1:3, the water- andoil-repelling properties are further improved.

EXAMPLE 10

As shown in FIG. 34, a hydrophilic substrate 51 is prepared. As thehydrophilic substrate, glass, ceramics, or metals such as Al and Cu orplastic may be used such that with the surface thereof is madehydrophilic. If a plastic or like substrate without any surface oxidefilm is to be used, the surface may be made hydrophilic, i.e., hydroxylgroups may be introduced into the surface, in advance by treating thesurface in an oxygen-containing plasma atmosphere at 100 W for 20minutes. The substrate is then coated by a casting process with amixture of fine particles 52 of silica with an average diameter of 10microns (for example "Microsheargel DF10-60A" or "-129A" by Asahi GlassCo., Ltd.) and silicate glass (for example "Hard Coating Agent KP-1100A"or "-1100B" by Shinetsu kagaku Co., Ltd. or "Si-8000" by Tokyo OhkaKogyo Co., Ltd.), the mixture being in a ratio of about 1:1, followed bythermal treatment at 500° C. for 30 minutes or plasma ashing at 300 Wfor 20 minutes. As a result, a glass layer 53 with surfaceirregularities at the micron level can be formed. Subsequently, anothercoating is formed using a non-aqueous solution containing a materialhaving a fluorocarbon group and a chlorosilyl group. For example asolution is prepared by dissolving 2% of

    CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 SiCl.sub.3

in a solution containing 90% of n-hexadecane and 1% of chloroform,followed by baking in a humidified atmosphere at 200° C. for 30 minutes.A dehydrochlorination reaction is brought about between chlorosilylgroups of the fluorocarbon chlorosilane-based surface active materialand --OH groups exposed at the surface of the glass layer 53, thusproducing --Si(O--)₃ bonds at the surface. In this way, afluorine-containing siloxane fluorocarbon-based polymer film 54 isformed on the glass layer having surface irregularities at the micronlevel. The film 54 is chemically bonded to the surface and has surfaceirregularities (FIGS. 35 and 36).

As an example, "DF10-60A" with a diameter of about 10 microns as thefine particles and "KP-1100A" as the silicate glass were dip coated andbaked at 350° C. A glass layer with surface irregularities of about 10microns was obtained.

Subsequently, a solution prepared by dissolving about 1% of CF₃ CH₂O(CH₂)₁₅ SiCl₃ in a solution containing 80% of n-hexadecane, 12 % ofcarbon tetrachloride and 8% of chloroform, was coated on the substratewith the polysiloxane coating film containing numerous --SiOH bonds atthe surface. The coated substrate was baked at 200° C. for 30 minutes.As a result, bonds of CF₃ CH₂ O(CH₂)₁₅ Si(O--)₃ were formed. Thus, afluorocarbon-based polymer film with surface irregularities of about 10microns and having a thickness of 1 to 5 microns, was formed (FIG. 38).This coating film 54 was difficult to separate in a checkerboard test.

By adding about 3% by weight as SiCl₄ as a crosslinking agent for thematerial containing a fluorocarbon group and a chlorosilane group to thesolution containing the material, the bonds of CF₃ CH₂ O(CH₂)₁₅ Si(O--)₃were crosslinked three-dimensionally by --Si(O--)₃. Thus, afluorocarbon-based polymer film having about double the hardness wasobtained (FIG. 38).

This fluorocarbon-based polymer film had surface irregularities of about10 microns, and its water contact angle was 130 to 140 degrees. Thewater 55 is shown in FIG. 36).

EXAMPLE 11

As in the preceding Example 10, a glass layer having desirable surfaceirregularities is formed on a substrate as shown in FIG. 34. The surfaceis then coated with an alcohol solution containing a material having afluorocarbon group and an alkoxysilane group. For example a solution isprepared by dissolving several % of

    CF.sub.3 (CF.sub.2).sub.n --R--SiY.sub.q (OA).sub.3-q

where n represents O or an integer, R represents an alkyl group, anethylene group, an acetylene group or a substituted group containing asilicon or oxygen atom, Y represents a hydrogen atom or a substitutedgroup such as an alkyl group, OA represents an alkoxyl group (Arepresenting a hydrogen atom or an alkyl group), and q represents 0, 1or 2, in methanol. The coated substrate the baked at 200° C. for about30 minutes. As a result, a dehydrochlorination reaction is brought aboutbetween alkoxyl groups of the fluorine-containing alkoxysilane-basedsurface active material and --OH groups exposed to the surface of theglass layer 53, thus producing -Si(O-)₃ bonds on the surface. Thus, afluorine-containing siloxane fluorocarbon-based polymer film 54 isformed on the irregular glass layer surface.

As an example, a solution was prepared by dissolving about 1% of CF₃ CH₂O(CH₂)₁₅ Si(OCH₃)₃ in an ethanol and coated on the substrate with thepolysiloxane coating film containing numerous --SiOH bonds at thesurface. The coated substrate was then baked at 200° C. for about 30minutes, thus producing bonds of

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 Si(O--).sub.3

A fluorocarbon-based polymer film with surface irregularities of about10 microns and a thickness of 1 to 5 microns was obtained. This coatingfilm was difficult to separate in a checkerboard test.

Further, by adding for example 5% by weight Si(OCH₃)₄ as a crosslinkingagent for the material containing a fluorocarbon group and analkoxysilane group to the solution containing the material, the bonds of

    CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 Si(O--).sub.3

were crosslinked three-dimensionally by --Si(O--)₃ bonds. Afluorocarbon-based polymer film was obtained which had about 2 to 2.5times the hardness of a coating film obtained without use of Si(OCH₃)₄.

Water drops 55 were allowed to fall onto this fluorocarbon-based polymerfilm with surface irregularities of about 10 microns. They contacted thefilm only at raised or projected portions thereof, as shown in FIG. 36.The film was very highly water-repelling, and its water contact anglewas about 135 to 140 degrees.

Further, by adding about 10% by weight of Si(OCH₃)₄ as a crosslinkingagent for the material containing a fluorocarbon group and analkoxysilane group to the solution containing the material, afluorocarbon-based polymer film having about four times the hardnesscould be obtained.

A similar coating process was carried out by adding 20% of fineparticles of a fluorocarbon-based polymer (i.e., polyethylenetetrafluoride) to the non-aqueous solution containing the materialcontaining a fluorocarbon group and an alkoxysilane group. Afluorocarbon-based polymer film was obtained which had excellentadhesion and was highly water-and oil-repelling, although the hardnesswas conventional.

By adding or incorporating an ethylene group or acetylene group into thealkyl chain portion, the coating film can be crosslinked afterwards byirradiating it with an electron beam of about 5 Mrads. A coating film isthus obtained with the hardness thereof increased by ten times.

EXAMPLE 12

As in Example 10, a glass layer 53 having surface irregularities wasformed on a substrate 51, as shown in FIG. 34. Then, a non-aqueoussolution was prepared by incorporating a material containing afluorocarbon group and a chlorosilane group. For example a solution wasprepared by dissolving about 1% of

    CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 SiCl.sub.3

in a solution containing 80% of n-hexadecane, 12% of carbontetrachloride and 8% of chloroform. The substrate provided with themonomolecular film containing numerous SiOH bonds at the surface wasdipped and held in the solution for about 30 minutes, thus producingbonds of

    CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 Si(O--).sub.3

on the surface. A fluorine-containing water- and oil-repelling film 56(i.e., chemically adsorbed monomolecular film) was formed. The film 56was chemically bonded to the glass layer and had surface irregularities(FIG. 37) at the micron level. This film did not separate in acheckerboard test. In this film, the fluorocarbon groups had regularorientation on the surface, providing very low surface energy, and thewater contact angle of the film was 135 to 145 degrees.

By adding or incorporating an ethylene group or acethylene group, intothe alkyl chain portion, the monomolecular film is subsequentlycrosslinked by irradiating it with an electron beam of about 5 Mrads,and thus the hardness can be further improved.

EXAMPLE 13

A processed glass plate 61 was washed with an organic solvent, andirregularities of about 0.1 micron were formed at its surface by sandblasting (FIG. 39). As another means for coarsening the surface, achemical etching process using fluoric acid or a rubbing process usingsand paper may be used. The permissible level of coarsening is withinthe visible light wavelength range. In this case, substantially allvisible light is transmitted.

As an example, a glass plate was dipped and held for about 2 hours in anon-aqueous solution containing a material containing a carbon fluoridegroup and a chlorosilane group. For example a solution was prepared bydissolving 1% by weight of CF₃ (CF₂)₇ (CH₂)₂ SiCl₃ in a solutioncontaining 80% of n-hexadecane (or toluene, xylene or disiclohexyl), 12%of carbon tetrachloride and 8% of chloroform. As a result, adehydrochlorination reaction was brought about between SiCl groups ofthe material containing a carbon fluoride group and a chlorosilane groupand hydroxyl groups numerously contained in the natural oxide filmformed on the glass plate, thus producing bonds of

    CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 Si(O--).sub.3

over the entire glass plate surface. A fluorine-containing monomolecularfilm 62 was formed. The film 62 was chemically bonded to the glass platesurface, and its thickness was about 1.5 nm (15 angstroms) (FIG. 40).The monomolecular film was firmly bonded by siloxane chemical bonds tothe substrate surface and did not separate. In a substrate comprising aplastic material, such as an acrylic acid resin or a polycarbonateresin, the same technique may be used by oxidizing the substrate surfaceto be hydrophilic by a plasma treatment at 300 W for about 10 minutesand using a freon solution in lieu of the surface active material.

The above processed glass plate was actually used to obtain greatreduction of the attachment of contaminants compared to a non-processedglass plate. Contaminant attached, if any, could be readily removed bybrushing with a brush. At this time, no scar or scratch was caused. Thewater wetting property was like that of lotus leaves, and the watercontact angle was about 155 degrees.

EXAMPLE 14

In this example, an aluminum plate is used, the surface of whichcontains less hydroxyl groups yet remains hydrophilic. The surface isformed with irregularities of about 0.2 microns by electrolytic etching.The surface irregularities may also be formed by other processes such asa chemical etching process using fluoric acid or a rubbing process usingsand paper. Again in this case, the surface irregularities may be withinthe visible light wavelength range. In this case, substantially allvisible light is transmitted. The same technique may be used for allmetals. In case of a plastic material such as an acrylic acid resin or apolycarbonate resin, the surface having been coarsened is oxidized to behydrophilic by a plasma treatment at 200 W for about 10 minutes.

The aluminum plate is then dipped and held for about 30 minutes in anaqueous solution containing a material containing a plurality ofchlorosilyl groups, e.g., a solution prepared by dissolving 1% by weightof SiCl₄, the molecules of which are small and have high activity tohydroxyl groups, in a chloroform solvent. The solution is highlyeffective for rendering the aluminum plate surface to be uniformlyhydrophilic. As a result, a hydrochloric acid removal reaction isbrought about owing to the presence of some --OH groups 72 at thealuminum plate surface 71 (FIG. 41), thus forming a siloxane-basedmonomolecular film. By using SiCl₄ as the material containing aplurality of chlorosilyl groups, a hydrochloric acid reaction is broughtabout on the surface of the aluminum plate 71 owing to hydrophilic --OHgroups exposed at the surface. The molecules are secured to the surfacevia --SiO-- bonds such as Cl₃ SiO-- and/or Cl₂ Si(O--)₂. By subsequentlywashing the system with a non-aqueous solution, e.g., chloroform, andthen with water, unreacted SiCl₄ molecules are removed, and a siloxanemonomolecular film 73 of (OH)₃ SiO-- and/or (OH)₂ Si(O--)₂ is obtainedon the aluminum plate surface (FIG. 42). The monomolecular film 73 thusformed is perfectly bonded to the aluminum plate by chemical bonds of--SiO-- and are difficult to separate. The film surface containsnumerous silanol (--SiOH) bonds corresponding in number to about threetimes the number of initial hydroxyl groups. As an example, the aluminumplate thus obtained, provided with the monomolecular film with numerous--SiOH bonds at the surface, was dipped and held for about one hour inan aqueous solution containing a material containing a carbon fluoridegroup and a chlorosilane group, e.g., a solution prepared by dissolvingabout 1% of

    CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 SiCl.sub.3

in a solution containing 80% of n-hexadecane, 12 % of carbontetrachloride and 8% of chloroform. As a result, bonds of

    CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 Si(O--).sub.3

were formed on the aluminum plate surface. A fluorine-containingmonomolecular film 74 thus was formed over the entire aluminum platesurface. It was chemically bonded to the inner siloxane monomolecularfilm and had a thickness of about 1.5 nm (15 angstroms) (FIG. 43). Itdid not separate in a peel-off test. Its water contact angle was about155 degrees.

Meanwhile, using a glass plate in lieu of the aluminum plate in theabove example 14, a hydrophilic coating film insoluble to organicsolvents and having a thickness of several microns was formed a surface(for instance the inner surface) which was desired to remain hydrophilicfor imparting with an anti-fogging effect. For example an aqueoussolution of polyvinylalcohol (poval) or pullulan was coated onto thesurface, before chemically adsorbing the material containing a carbonfluoride group and a chlorosilane group. After the adsorption, thehydrophilic coating film was removed by water washing, thus obtaining atransparent glass plate, which had a water- and oil-repellinganti-contaminating monomolecular film 74 formed on its outer surface. Amonomolecular film (or siloxane film) 73 having hydrophilic hydroxylgroups was formed on its inner surface, as shown in FIG. 44. Theanti-fogging effect of this glass plate was checked to find that itssurface remained hydrophilic and was readily wetted by water and did notfog. By adsorbing a composition obtained by combining two differentsurface active materials with different molecular lengths, surfaceirregularities were obtained at the molecular level, thus furtherimproving the water- and oil-repelling properties and further enhancingthe anti-contaminating effects. As shown above, in this example a glassplate or like material is formed with surface irregularities of about0.1 micron (μm). The material is dipped in, for example, afluorine-containing chlorosilane-based surface active agent diluted inan organic solvent. As a result, a hydrochloric acid removal reaction isbrought about owing to numerous hydroxyl groups contained at the surfaceof a natural oxide film formed on the surface of the glass plate or thelike. A carbon fluoride-based monomolecular film is thus formed on thesubstrate surface via siloxane bonds. In this way, surfaceirregularities less than the visible light wavelength range (400 nm) areformed on the substrate surface, and a carbon fluoride-basedmonomolecular film with a thickness of a nanometer level is formed onthe substrate surface via siloxane bonds, thus obtaining a very highlywater- and oil-repelling anti-contaminating film without spoiling theluster of the substrate itself.

EXAMPLE 15

As shown in FIG. 45, a polyethylene-trifluorochloride film 81 with athickness of 100 to 200 microns (μm) was prepared and held in a vacuumchamber at 10⁻¹ to 10⁻² Pa. Then, its surface was spatter etched in anoxygen-containing plasma atmosphere by RF glow discharge.

This process was carried out with a discharge power density of 0.15W/cm² for 1 to 10 minutes, thus forming surface irregularities of about0.1 micron. The film did not become opaque (FIG. 45(a). Actually, thesurface coarseness may be less than 0.3 micron, which is sufficientlysmall compared to the wavelength of visible light. Under this condition,the film did not become opaque. The etching condition may beappropriately selected. Subsequently, the film with the surface thereofcoarsened was dipped and held for one hour in a non-aqueous solutioncontaining a material having a fluorocarbon group and a chlorosilanegroup. For example an "Aflood" (a fluorine-based solvent by Asahi GlassCo.,Ltd.) solution was prepared by dissolving about 5% of a materialrepresented by the formula:

    CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 SiCl.sub.3

As a result, a dehydrochlorination reaction is brought about on the filmsurface having been etched in an oxygen plasma owing to hydroxyl (--OH)groups formed at the surface, thus producing bonds represented by theformula [3]: ##STR3## on the film surface. The film was then washed with"Aflood" to remove the unreacted material remaining on the surface,followed by washing with water or exposing to air containing moisture.The --SiCl group was changed to a --SiOH group as the formula [4].##STR4##

Each silanol group (--SiOH) was then dehydrated and crosslinked to forma siloxane bond (--SiO--) after drying as the formula [5]. Dryingtemperature may be room temperature or above. ##STR5##

The adsorbed monomolecular film 82 has a fluorine group and ischemically bonded (i.e., covalently bonded) to the substrate 1. Thechemical bond is via a siloxane bond. The formation of chemicallyadsorbed monomolecular film 3 was assumed by FTIR spectrometry and thethickness was about 1.5 nanometers (nm). It is firmly bonded such thatit will not separate. A fluorine-contaiing monomolecular film 82 wasformed which was chemically bonded to the surface and had surfaceirregularities at the micron level.

FIG. 45(b) is an enlarged schematic view showing part E in FIG. 45(a).In this case, fluorocarbon groups were formed in a regular orientationon the surface, and the surface energy was extremely low. The watercontact angle was 135 to 145 degrees.

EXAMPLE 16

A polyethylene terephthalate film 91, for example, was prepared and heldin a vacuum chamber at 10⁻¹ to 10⁻² Pa. Then, the film surface wasspatter etched in an oxygen-containing plasma atmosphere based on RFglow discharge, the process was carried out with a discharge powerdensity of 0.1 W/cm² for 1 to 5 minutes, thus forming surfaceirregularities. The surface coarseness obtained was about 0.1 micron,and the film did not become opaque. Actually, the film would not becomeopaque as so long as the surface coarseness is less than 0.3 micron. Theetching condition may be appropriately selected. With a film which neednot be transparent, it was possible to coarsen the surface to aboutseveral tens of microns to obtain sufficient effects.

The film with the surface thereof coarsened was then dipped and held forabout one hour in an "Aflood" solution (a fluorine-containing materialby Asahi Glass Co., Ltd.) prepared by dissolving about 5% of SiCl₄ intothe "Aflood". As a result, a dehydrochlorination reaction is broughtabout on the film surface having been etched by oxygen plasma owing tohydroxyl (--OH) groups 92 contained at the surface, as shown in FIG.46(a). Thus, molecules represented by formulas 6 and 7 ##STR6## aresecured to the film surface via --SiO-- bonds.

By subsequently washing the system with a non-aqueous solvent, e.g.,"Aflood" (a fluorine-based solvent by Asahi Glass Co., Ltd., and thenwith water, SiCl₄ molecules which did not react with the film wereremoved. A siloxane monomolecular film 93 represented by a formula 8 orformula 9 ##STR7## was obtained, as shown in FIG. 46(b). It ischemically bonded.

As an example, the film provided with the monomolecular film as notedabove was dipped and held for about one hour in a non-aqueous solutioncontaining a material having a fluorocarbon group and a chlorosilanegroup, e.g., a solution prepared by dissolving about 3% of a materialrepresented by formula:

    CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 SiCl.sub.3

in "Aflood" (a fluorine-containing solvent by Asahi Glass Co., Ltd.). Asa result, a dehydrochlorination reaction was brought about owing tonumerous hydroxyl (--OH) groups contained at the film surface, thusproducing bonds represented by the formula:

    CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 Si(O--).sub.3

on the film surface. A fluorine-containing monomolecular film 94 wasformed as shown in FIG. 46(c). The film thus obtained was chemicallybonded and had surface irregularities at the micron level. It had highdensity compared to the film in Example 15.

This monomoecular film will not separate in a checkerboard test. Inaddition, fluorocarbon groups were oriented on the surface, and thesurface energy was extremely low. The water contact angle was 140 to 150degrees.

Further, using an adhesive, a glass plate was applied to the backsurface of the water- and oil-repelling film thus obtained. A verywater- and oil-repelling and highly transparent glass plate wasobtained. Contaminants did not attach without difficultly, and could beeasily removed. Thus, the glass plate was very highly practical.

As in the above example, a chlorosilane-based surface active materialcontaining a chlorosilane (SiCl_(n) X_(3-n), n representing 1, 2 or 3, Xrepresenting a functional group) group at one end and a straight chaincarbon fluoride group at the other end is chemically adsorbed viasiloxane bonds to a film surface having been coarsened on the order ofsub-microns to microns by means of etching, sand blasting or a moldapplication process, thus forming a carbon fluoride chemically adsorbedmonomolecular film. The film is highly water- and oil-repelling and doesnot separate. The coarseness of the film surface is on the order ofsub-microns to microns, and the thickness of the monomolecular film isat the namometer level. Thus, the film has an excellent lighttransmission property, does not hinder optical characteristics of thefilm and is excellent in durability.

By adding or assembling a vinylene group or ethylene group to the alkylchain portion, the monomolecular film is crosslinked after formation byirradiating it with an electron beam of about 5 Mrads. Thus, hardness isimproved.

According to the invention, a very highly water- and oil-repellingcarbon fluoride-based chemically adsorbed monomolecular film may beformed on a film surface by a method which comprises a step ofcoarsening the film surface on the order of sub-microns to microns inadvance by means of etching, sand blasting or a mold application processand a step of forming on the film surface a chemically adsorbedmonomolecular film by chemically adsorbing a chlorosilane-based surfaceactive material containing a chlorosilane group, SiCl_(n) X_(3-n),(where n represents 1, 2 or 3, X represents a functional group) at oneend and a straight chain carbon fluoride group at the other end.

Further, a fluorine-containing carbon fluoride-based chemically adsorbedmonomolecular film having a relatively high molecular adsorptiondensity, can be obtained by a method which comprises, subsequent to thestep of coasening the film surface on the order of sub-microns tomicrons by means of etching, sand blasting a mold application process, astep of contacting the coasened film surface with a non-aqueous solutioncontaining a material containing a plurality of chlorosilyl groups tocause a reaction between hydroxyl groups at the film surface and thechlorosilyl groups of the material containing a plurality of chlorosilylgroups and a step of removing excess material containing a plurality ofchlorosilyl groups remaining on the film by washing with a non-aqueousorganic solvent and then reacting with water, before the step of forminga monomolecular film of the material containing a plurality of silanolgroups and the step of forming an accumulation of the chemicallyadsorbed monomolecular film by chemically adsorbing a chlorosilane-basedsurface active material containing a chlorosilane group at one end and astraight chain carbon fluoride group at the other end to the filmsurface.

The coarseness of the film surface is on the order of sub-microns tomicrons, preferbly 0.3 microns or less. In this case, an excellent lighttransmission property is obtained, and light transmission properties ofthe film in the visible light wavelength range are not hindered. If thecoarseness of the film surface is greater than 0.3 microns, the water-and oil-repelling properties are not adversely affected, althoughoptical characteristics are slightly sacrificed. Thus, even in thiscase, the film can find extensive applications. The surface coarsenessis suitable for use in light-blocking films or frost glass.

Further, the film may be readily applied by an adhesive on its backsurface to an intended object without adversely affecting opticalcharacteristics. A peel-off sheet may be present on the surface of theadhesive.

The water- and oil-repelling film according to the invention may beapplied to glass products such as vehicle windows or font glasses, glasslenses and building windows glasses, ceramic products such as porcelainarticles, dishes, vases and water tanks, metal products such as sashes,doors and exterior walls of buildings, furniture, cover films, etc.Examples of the film are fluorine resin-based films of poly(ethylenetrifluorochloride), etc., polyester-based films of poly(ethyleneterephthalate), etc., polyimide-based films, polyamide-based films ofnylon, etc., polyethylene films and polypropyrene films. The waterwetting property was like that of lotus leaves, and the water contactangle was about 155 degrees.

As has been shown, the invention is greatly beneficial to industry.

The invention may be embodied in other specific forms without departingfrom the spirit or essential characteristics thereof. The presentembodiment is to be considered in all respects as illustrative and notrestrictive, the scope of the invention being indicated by the appendedclaims rather than by the foregoing description and all changes whichcome within the meaning and range of equivalency of the claims areintended to be embraced therein.

What is claimed:
 1. A method of manufacturing a water- and oil-repellingadsorbed film comprising:making a substrate surface irregular whereinthe irregularities have a diameter of 0.01-50 μm; and contacting saidirregular surface with a non-aqueous solution containing an activesurface material comprising molecules having a fluorocarbon group and achlorosilane group or having a fluorocarbon group and an alkoxysilanegroup.
 2. The method of forming a water- and oil-repelling adsorbed filmaccording to claim 1,further comprising providing the substrate surfacewith surface active hydrogen groups before or after the step of makingthe substrate surface irregular; wherein the contact step is carried outby contacting the substrate surface with a silane-based surface activematerial with the molecules thereof containing a chlorosilane oralkoxysilane group at one end and a fluorocarbon group at the other endto adsorb said surface active material to the substrate surface by adehydrochlorination reaction or a dealcoholation reaction; formingthereon an outer layer more remote from the substrate by reacting theadsorbed surface active material with water with or without previousremoval of non-reacted surface active material by washing using anon-aqueous organic solution; and drying the substrate surface.
 3. Themethod of forming a water- and oil-repelling adsorbed film according toclaim 1, further comprising;providing the substrate surface with activehydrogen groups before or after the step of making the surfaceirregular; wherein the contacting step is carried out by contacting thesubstrate surface with a non-aqueous solution containing a surfaceactive material with the molecules thereof having a plurality ofchlorosilyl groups to adsorb said surface active material by adehydrochlorination reaction; reacting the adsorbed surface activematerial with water with or without previous removal of non-reactedsurface active material by washing with a non-aqueous organic solutionto form an inner layer; contacting the surface of said inner layer witha silane-based surface active material with the molecule thereofcontaining a silyl group at one end and a fluorocarbon group at theother end to adsorb said surface active material to the substratesurface by a dehydrochlorination reaction or a dealcoholation reaction;forming thereon an outer layer more remote from the substrate byreacting with water with or without previous removal of non-reactedsurface active material by washing with a non-aqueous organic solution;and drying the substrate surface.
 4. The method of manufacturing awater- and oil-repelling adsorbed film according to claim 1, whereinsaid step of making the substrate surface irregular is carried outby:mixing fine particles and silicate glass on the substrate surface toform a coating and then thermally baking said coating together with thesubstrate and then performing a procedure selecting from the groupconsisting of electrolytic etching, chemical etching, sand blasting,spattering, depositing, and rubbing.
 5. The method of manufacturing awater- and oil-repelling adsorbed film according to one of claims 2 and3, wherein said surface active material is one with the moleculesthereof having at one end a chlorosilane group represented by a formula;

    --SiCl.sub.n X.sub.3-n

where n represents an integer from 1 to 3, and X represents at least onefunctional group selected from the group consisting of a lower-alkylgroup and a lower-alkoxyl group.
 6. The method of manufacturing a water-and oil-repelling adsorbed film according to one of claims 2 and 3,wherein said surface active material is a compound selected from a groupconsisting ofCF₃ --(CF₂)_(n) --T--SiY_(p) Cl_(3-p) where n represents aninteger from 1 to 25, T represents a member of the group consisting ofan alkylene group, an ethylene group, an acetylene group and asubstituted group containing a silicon atom and a hydrogen atom, Yrepresents a substituted group selected from the group consisting of analkyl group, a cycloalkyl group, an aryl group and derivatives of thesegroups, and p represents a number selected from the group consisting of0, 1 and 2, and CF₃ --(CF₂)_(n) --T'--SiZ_(q) (OA)_(3-q) where nrepresents either O or an integer, T' represents a member of the groupconsisting of an alkylene group, an alkyne group, and a substitutedgroup containing a silicon atom and a hydrogen atom, Z represents asubstituted group selected from a group consisting of an alkyl group, acycloalkyl group, an aryl group and derivatives thereof, A represents ahydrogen atom or an alkyl group, and q represents 0, 1 or
 2. 7. Themethod of manufacturing a water- and oil-repelling adsorbing filmaccording to claim 3, wherein said surface active material with themolecules thereof containing a plurality of chlorosilyl groups is acompound selected from the group consisting of SiCl₄, SiHCl₃, SiH₂ Cl₂,and Cl--(SiCl₂ O)_(n) --SiCl₃, where n is an integer from 1 to
 10. 8.The method of manufacturing a water- and oil- repelling adsorbed filmaccording to claim 1, wherein said substrate is a plastic substrate andthe method further comprises contacting the surface thereof with anoxygen-containing plasma atmosphere to be hydrophilic.
 9. The method ofmanufacturing a water- and oil-repelling adsorbed film according to oneof claims 2 and 3, wherein said active hydrogen group on the substratesurface is a member of the group consisting of a hydroxyl group, anamino group and an imino group.
 10. The method of manufacturing a water-and oil-repelling adsorbed film according to claim 3, wherein saidnon-aqueous solution containing a surface active material contains acrosslinking agent selected from the group consisting of SiP_(s)Cl_(4-s) where P represents H, a lower-alkyl group and a lower-alkoxylgroup, and s represents of 0, 1 and 2, and SiQ_(t) (OA)_(4-t) where Q isat least one substituted group selected from the group consisting of alower-alkyl group and a lower-alkoxyl group, A represents hydrogen atomor a lower-alkyl group, and t represents 0, 1 or
 2. 11. The method ofmanufacturing a water- and oil-repelling adsorbed film according toclaim 1, wherein the irregularities have a diameter of 0.5-50 μm. 12.The method of manufacturing a water- and oil-repelling adsorbed filmaccording to claim 11, wherein the irregularities have a diameter of1-10 μm.
 13. A method of manufacturing a water- and oil-repellingadsorbed film comprising:preparing a substrate having active hydrogengroups at the surface and contacting said substrate with a non-aqueoussolution containing a material with the molecules thereof having aplurality of chlorosilyl groups to coat said material onto the surfaceof said substrate through a reaction between active hydrogen groups atsaid substrate surface and the chlorosilyl groups of said material withthe molecules thereof having a plurality of chlorosilyl groups; coatingwith a non-aqueous solution containing a mixture of a surface activematerial with the molecules thereof containing a fluorocarbon group anda chlorosilane group and fine particles having a hydrophilic surface;contacting with a mixture of a material with the molecules thereofcontaining a fluorocarbon group and an alkoxysilane group and fineparticles having hydrophilic surface; and thermally baking said coatingtogether with the substrate.
 14. A method of manufacturing a water- andoil-repelling adsorbing film comprising:a step of preparing a substratehaving active hydrogen groups at the surface and contacting the surfaceof said substrate with a non-aqueous solution containing a material withthe molecules thereof containing a plurality of chlorosilyl groups toadsorb said material to the substrate surface through a reaction betweenactive hydrogen groups on the substrate surface and chlorosilyl groupsof said material with the molecules thereof having a plurality ofchlorosilyl groups; forming a thin film or a chemically adsorbedmonomolecular film of said material with the molecules thereofcontaining a plurality of chlorosilyl groups on said substrate with orwithout removal of non-reacted material remaining on the substrate bywashing with a non-aqueous organic solution; adsorbing on to the film anon-aqueous solution containing a mixture of a surface active materialwith the molecules thereof having a fluorocarbon group and a silyl groupand fine particles having hydrophilic surface; and thermally baking saidcoating together with the substrate.